Journal Pre-proof

Recent innovations in functionalized layered double hydroxides:

Fabrication, characterization, and industrial applications

Shadpour Mallakpour, Masoud Hatami, Chaudhery Mustansar

Hussain

PII: S0001-8686(20)30307-9
DOI: https://doi.org/10.1016/j.cis.2020.102216
Reference: CIS 102216

To appear in: Advances in Colloid and Interface Science

Revised date: 25 July 2020

Please cite this article as: S. Mallakpour, M. Hatami and C.M. Hussain, Recent innovations
in functionalized layered double hydroxides: Fabrication, characterization, and industrial
applications, Advances in Colloid and Interface Science (2019), https://doi.org/10.1016/
j.cis.2020.102216

This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
not yet the definitive version of record. This version will undergo additional copyediting,
typesetting and review before it is published in its final form, but we are providing this
version to give early visibility of the article. Please note that, during the production
process, errors may be discovered which could affect the content, and all legal disclaimers
that apply to the journal pertain.

© 2019 Published by Elsevier.

 Journal Pre-proof

Revised

Recent innovations in functionalized layered double hydroxides: Fabrication,

characterization, and industrial applications

Shadpour Mallakpour a,*, Masoud Hatami a, Chaudhery Mustansar Hussain b

a
Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan

University of Technology, Isfahan, 84156-83111, I. R. Iran

b
Department of Chemistry and Environmental Science, New Jersey Institute of

of
Technology, Newark, N J 07102, USA

ro
-p
ABSTRACT
re
Layered Double Hydroxides (LDHs) are a group of hydrotalcite-like nano-sized

materials with cationic layers and exchangeable interlayer anions. The wide range of
lP

divalent and trivalent cationic metals and anionic compounds are employed in the
na

synthesis of LDH materials, which have improved their importance among the

researchers. Because of their high anion exchange property, memory effect, tunable
ur

behavior, bio-friendly, simple preparation, and their affordability, these nano-materials

Jo

are essentially interested today. Modification of LDHs improves their behaviours to

make them appropriate in industrial fields, including biological, adsorbent, mechanical,

optical, thermal, electrical fields, etc. This review has critically discussed the structural

features, main properties, and also clarified the most important methods of modification

and intercalation of LDH nano-materials. Moreover, some novel reported researches

related to the successful modification of LDH materials have been characterized and

*
Corresponding Author at: Organic Polymer Chemistry Research Laboratory, Department of Chemistry,
Isfahan University of Technology, Isfahan, 84156-83111, I. R. Iran. Tel.; +98-31-3391-3267; FAX: +98-
31-3391-2350.
E-mail address: mallak@iut.ac.ir, mallak777@yahoo.com. (S. Mallakpour)

1
 Journal Pre-proof

briefly the advantages, disadvantages, and applications are presented in the industrial

fields.

Keywords:

Layered double hydroxide

Modification

Intercalation

Characterization

of
Application

ro
-p
Contents
re
1. Introduction

2. Structure of LDH material

lP

3. Properties of LDH samples

na

3.1. Morphological properties

3.2. Thermal stability

ur

3.3. Anion exchange capacity

Jo

3.4. Memory effect

4. Synthesis and characterization of the modified LDHs

4.1. Coprecipitation method

4.2. The effect of ultrasound irradiation in the coprecipitation method

4.3. Anion exchange method

4.4. Hydrothermal method

4.5. Urea hydrolysis

4.6. Microwave method

2
 Journal Pre-proof

4.7. Sol-gel method

5. Applications of the modified LDHs

5.1. Modified LDH/polymer nanocomposites (NCs)

5.2. Antibacterial application

5.3. Removal of pollutants

5.4. Anti-corrosion application

5.5. Drug delivery application

5.6. Catalytic application

of
5.7. Photocatalytic application

ro
5.8. Bioactive application -p
5.9. Solar cell application
re
6. Conclusions and future challenges

Acknowledgments
lP

Appendix A. Nomenclature
na

References
ur

1. Introduction
Jo

Recently, studies in green chemistry have designed novel and bio-friendly materials

and methods to eliminate or reduce the side effects of chemical materials. Bio-safe and

eco-friendly nano-materials expose the superior applications, owing to their individual

behaviors [1, 2]. The applications and properties of nanostructured materials not only

are depended on their compositions but are dependent on their other properties such as

shape, structure, phase, and size distribution as well [3, 4]. Nowadays, Layered Double

Hydroxide (LDH), known as anionic clays, has been considered as an interesting type of

hydrotalcite-like compounds in both academia and industry [5-7]. These materials are

3
 Journal Pre-proof

low-priced and have significant features such as resistance to thermal changes and pH

variations, tunable interior architecture, high surface area, and great anion-exchange

treatments [8, 9]. Besides, LDHs are known as a novel developing type of crystalline

clustered compounds to form multifunctional nano-sized samples [10, 11]. However,

just similar to the other inorganic nano-hybrids, the use of LDHs is restricted due to

their large charge density and high hydrophilic nature. Therefore, these materials cannot

extensively interact with other molecules containing hydrophobic linkages, and intra-

molecular interactions of them increased their aggregation [12, 13]. In addition, pure

of
LDHs do not show very remarkable applications in modern technology [14, 15]. Hence,

ro
to develop their organophilic nature, to enlarge their basal spacing, and to promote their
-p
applications in industrial fields, interlayer space and the surface of LDHs can be well
re
modified with appropriate organic and inorganic modifying agents [16, 17].

Accordingly, in recent years, modification of LDHs has been a significant interest for
lP

scientists, and according to the Scopus database more than 500 documents have been
na

published only in the last decade (2010 to 2020) (Fig. 1A), which classify in different

types such as article (89.4%), review (5.4%), conference paper (3.2%), book chapter
ur

(1.2%), conference review (0.8%) (Fig. 1B). As Fig. 1A shows, in recent years attention
Jo

on the modified LDHs are increased and researchers have noticeably studied these

materials.

Our aim in this study is to review the importance and applications of modified

LDHs as significant nano-materials that recently were extensively considered in both

academia and industry. We will comprehensively discuss the main synthesis methods,

structural aspects, properties, and characterization of these materials. Furthermore, we

will briefly clarify the major applications and the advantages and disadvantages of the

modified LDHs.

4
 Journal Pre-proof

of
ro
-p
re
lP
na

Fig. 1. Diagrams observed about (a) modification of LDH in the range of 2010-2020
ur

and (b) documents by type for modified LDH based on the Scopus database (These data
Jo

were obtained on April 14, 2020).

2. Structure of LDHs

LDHs, as a general and widespread group of inorganic flaked nano-hybrids with

the large ability of anionic modification, have been recognized for over 150 years [18].

These materials, which have been clarified as the family of anionic clay firstly were

studied in Sweden in 1842 [19]. The hydrotalcite crystal structure of LDHs is

5
 Journal Pre-proof

constructed of the stacking of the positive charged layers [18, 20], and LDHs usually are

denoted by the following common formula (Equation 1):

[M1-x2+Mx3+(OH)2]x+.Ax/nn-·mH2O (1)

where M2+ and M3+ are divalent cationic metals (such as Mg2+, Zn2+, Cu2+, Co2+, etc.)

and trivalent cationic metals (such as Al3+, Fe3+, Mn3+, Cr3+, etc.), respectively. A is an

exchangeable anion into the octahedral layers, and x is molar ration and is denoted with

the M3+/(M2++M3+) ratio [18, 21]. In the LDH materials, M2+ can be exchanged with

M3+, which creates the positive residual charges of layers, and these charges can be

of
neutralized with the anionic molecules between the layers [22]. As revealed in the LDH

ro
structure (Fig. 2), water molecules attach layers with each other through hydrogen
-p
bonding [23].
re
lP
na
ur
Jo

Fig. 2. Schematic structure of LDH. Fig. adapted with permission from: Ref. [18].

3. Properties of LDH samples

6
 Journal Pre-proof

Due to the various arrangements and preparation methods of LDHs, these samples

show a variety of properties. Herein, it will be argued some of the appropriate features

that support and facilitate LDH requests in nature.

3.1. Morphological properties

Morphological behaviours, surface area, particle size, and porosity of LDHs are

extremely necessary to describe their structure. Shape, morphology, and exact surface

area of LDHs are determined by conditions and methods of preparation [24-26].

of
According to the reported research by Benico et al. [23], the exact surface area of LDHs

ro
is extensively between 50 and 200 m2 g-1, while it was observed 425 m2 g-1 in a research
-p
studied by Yu et al. [27]. The layered structure of LDHs changes to the oxides or a
re
mixture of oxides under calcination of them at a particular temperature, which changes

their morphology [23, 28]. Also, the porosity of the prepared LDHs changes
lP

significantly into the microporous to the mesoporous range, and their particle size is
na

different owing to various composition and crystallinity differences [29, 30].

ur

3.2. Thermal stability

Jo

The thermal behavior of nano-materials is one of the other important properties

of them. In LDHs, this parameter is usually discussed with thermogravimetric analysis

(TGA), residue mass at final temperature (char yield), and differential scanning

calorimetry (DSC). The thermal decomposition steps of LDHs are mostly discussed and

the precise temperature range for each step is dependent on several factors such as the

type of LDH (including types of cationic metals and anionic interlayer, molar ratio,

etc.), heating rate, and inert atmosphere (N2 or O2) [23, 31]. The decomposition of

fabricated LDHs usually occurs in two main steps of mass loss. The first step that

7
 Journal Pre-proof

occurs at ambient temperatures to 170 oC is outstanding to the losing of physically

adsorbed water, and the second step that occurs at 190-650 °C is related to LDH

dihydroxylation (forming water as a product) and decomposition of intercalated anions

[32]. Also, it is observed that the organic intercalation of LDH decreased its thermal

stability [23].

3.3. Anion exchange capacity

An appropriate feature of LDHs is their high anion exchange capacity, which

of
depends on many factors such as the cationic metals ration, capability of the applied

ro
anion for stabilizing layer building, and molecular mass of both cations and anions [33,
-p
34]. One study indicated that the anion exchange capacity of LDHs is between 200 and
re
450 cmolc kg-1 [23]. LDH interlayer anions can simply substitute with the other

negatively-charged molecules, and the favorite order of usual and public inorganic
lP

anions is as follows [35]:

na

NO3- < Br- < Cl- < F- < OH- < SO42- < CO32-

This order displays that NO3- as a common inorganic anion can simply exchange
ur

with more powerful anions like CO32-. A general mechanism of anion exchange
Jo

property can be indicated as shown below (Equation 2):

LDH.Am-+Xn-→LDH.Xn-+Am- (2)

where A and X are the host and guest anions with negative charges of m and n,

respectively [36].

3.4. Memory effect

One interesting property of the LDHs is associated with the memory effect

feature of them. When they heated at high temperatures (more than 400), they lose their

8
 Journal Pre-proof

water molecules and other organic segments in their structure. Thus, they lose their

layer structure and produce the metal oxides, and they are known as layered double

oxide (LDO). However, when these samples are immersed in a proper solution such as

water, they reconstruct their layer structure and produce LDH again [37, 38]. However,

with this feature, pure LDHs can be produced.

4. Synthesis and characterization of the modified LDHs

LDHs are generally prepared at industrial scales by cost-effective and eco-

of
environmentally approaches. These materials are fabricated with an extensive range of

ro
divalent and trivalent cations combined with the different interlayer anions [6, 39].
-p
Numerous factors must be considered for synthesis of LDHs, such as the degree of M2+
re
exchanged by M3+, nature of metallic cation and interlayer anion, pH condition,

atmosphere control, and method of fabrication [40, 41]. Also, the crystalline structure,
lP

morphological properties, surface area, and distribution particle size of them change
na

under the described parameters [6]. In addition, it is observed that the fabricated LDHs

containing different physical properties have different capabilities to be used in

ur

industrial fields [42]. The microstructure, crystallinity, composition, and morphology of

Jo

the modified LDHs are characterized with various spectroscopic analyses including

Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), TGA, Energy

dispersive X-ray (EDX) spectroscopy, Atomic force microscopy (AFM), Field emission

scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM),

Brunauer-Emmett-Teller (BET) theory, etc. Hence, we tried to devote this section to the

most important methods for the preparation of LDHs, and also some researches related

to each method are expressed.

9
 Journal Pre-proof

4.1. Coprecipitation method

Coprecipitation is one of the simplest, low-priced, and reliable procedures for

the construction of LDHs [42, 43]. Typically, a mixed aqueous solution of two different

metal salts (M2+ and M3+) is prepared and slowly added to a solution of base-containing

guest species over hours under an inert atmosphere with vigorous stirring [44, 45]. In

this method, to avoid the formation of M(OH)2 and M(OH)3 impurities, it is essential to

control the pH of the solution [46]. With this method, the different cationic metals (with

obvious molar ratio) and interlayer anions can be used for the fabrication of LDH, and

of
the pH of the solution is usually sustained among 7 to 10.

ro
In a research studied by Lyu et al. [47], the coprecipitation method was
-p
considered for intercalation of the LDH (Mg2+/Al3+ = 2) with stearate molecule.
re
Although the stearate increased the LDH interlayer space (1.69 nm) but decreased its

crystallinity compared to pure MgAl-LDH with an interlayer space of 0.78 nm.

lP

Also, negative charged vitamin C (VC) was encapsulated effectively into the
na

interlayers of Ca/Al LDH via the coprecipitation procedures with a molar ratio of

Ca2+/Al3+ = 3 [48]. The XRD pattern of pure Ca2Al-NO3 displayed the reflection peaks
ur

related to the well-crystallized layers; a sharp and symmetrical peak at lower 2θ (about
Jo

11.0o) and a weak peak at greater 2θ (about 21.0o), and also its gallery height was about

8.8 A. After the intercalation of LDH with an organic compound, the XRD pattern of

Ca2Al-VC shifted to lower angle position (2θ = 6.0o) with the interlayer space of 14.6 A

(Fig. 3). Thus, with the basal distance of 9.8 A, it was recommended that the negative

charged VC molecule was vertically intercalated between the LDH layers.

10
 Journal Pre-proof

of
ro
Fig. 3. The results of XRD for (a) pure Ca2Al-NO3 and (b) VC modified Ca2Al. Fig.
-p
adapted with permission from: Ref. [48].
re
lP

Cardanol-BS modified LDH nano-hybrid was produced using the coprecipitation

as a non-expensive and simple method by Wang et al. [49]. The cardanol-BS altered the
na

mass loss steps in TGA thermogram, and in truth changed the thermal behavior of LDH;
ur

confirming the existence of organophilic molecules in the LDH structure.

In a research, the coprecipitation procedure was applied for the intercalation of

Jo

LDH with triethoxyvinylsilane (TEVS) to form durable bonds and increase its active

sites to interact with polymeric resins [50]. The FT-IR spectrum confirmed the

modification of LDH with TEVS through its new adsorption bands in structure. Also,

ultraviolet (UV)-visible analysis exhibited that the TEVS molecule promoted UV

performance and absorptive capacity of the LDH in comparison with the unmodified

LDH. Moreover, the SEM image disclosed a little aggregating state of nanostructured

layers in TEVS modified LDH.

11
 Journal Pre-proof

Recently, the coprecipitation was selected as a simple method to intercalate

carboxymethyl-modified cyclodextrin into the LDH structure [51]. For this purpose, it

was important to control the pH of the formed solution and fixed at 10. Also, the

prepared LDH with the ratio of Zn2+/Al3+ = 2 showed a good crystallinity.

4.2. The effect of ultrasound irradiation in the coprecipitation method

Currently, ultrasound irradiation has received much attention because this technique

is low-priced, harmless, non-toxic, and can be widely used for the homogeneous

of
dispersion of LDH materials. It is due to the high pressure and temperature that is

ro
produced during the sonication [52, 53]. Also, with ultrasonic irradiation, the reaction
-p
time is decreased compared to the mechanical techniques [54]. Thus, the described
re
features are good factors to select the ultrasonic instrument as a fascinating approach to

be applied in the synthesis of LDHs in comparison with the conventional methods.

lP

For example, Mallakpour et al. [55] intercalated Mg/Al-CO32--LDH with

na

biodegradable anionic diacid containing tetrabromophthalic anhydride and L-aspartic

acid using the coprecipitation method at pH = 10 using applying the ultrasonic

ur

irradiation as a green and safe tool. The additional observed bands at 1720, 1124, and
Jo

1389 cm-1 in the FT-IR spectrum of diacid modified LDH confirmed the presence of

organic spacers of diacid in the LDH structure.

Also, Baruah et al. [56] used the probe-sonication technique to modify synthesized-

LDH with N-doped graphene oxide (NGO) to make a highly efficient adsorbent for the

elimination of deadly metallic cations [Cd(II) and Pb(II) ions]. As shown in SEM

images (Fig. 4), only 10 min sonication was sufficient to change the LDH morphology;

the size of sheets was lower, and their dispersity was higher in LDH/NGO.

12
 Journal Pre-proof

Fig. 4. SEM images of (a) NiFe-CO3-LDH, (b) NGO and (c) NiFe-CO3-LDH-NGO

composite. Fig. adapted with permission from: Ref. [56].

of
ro
The intercalation of methotrexate (MTX) into the Mg-Al-LDH using the

sonication technique was reported by Liu et al. [57]. Firstly, at room temperature, LDHs
-p
were delaminated as 2D nanosheets by the ultrasonic irradiation treatment, and then
re
these nanosheets were reassembled into the MTX matrix to arrange the MTX
lP

intercalated LDH hybrids. This process focused on the simple, non-expensive, and short

procedures for modification of LDHs. Also, modification of the LDH with the MTX
na

enhanced its thermal behavior.

ur

4.3. Anion exchange method

Jo

This method is based on two kinds of anions: guest anion and host anions.

Commonly, in the anion exchange method, the host anions are exchanged with the guest

anions in the basal spacing of LDH. Also, in order to limit the carbonate anions of the

atmosphere, the process is usually done under an inert atmosphere [23, 46, 58, 59].

Likewise, the role of pH is very important, and both anionic guest materials and LDH

layers should be stable against pH [37, 60]. This method is preferred in some conditions

in which the coprecipitation is not good such as direct interactions between the

13
 Journal Pre-proof

interlayer anions and cationic metals, and high solubility of cations and anions in the

basic solution [61, 62].

For example, chiral organic diacid intercalated LDH was synthesized using an

ion exchange process based on MgAl-CO32-LDH and N,N-(pyromellitoyl)-bis-L-

isoleucine by Mallakpour and Dinari [63]. The unmodified LDH disclosed the plate-like

structure with lateral dimensions about micrometer and thickness fewer than a hundred

nanometer (Fig. 5a and b). After optically active modified LDH, the FE-SEM images

showed a more floppy structure in comparison to the pure LDH (Fig. 5c and d).

of
ro
-p
re
lP
na
ur
Jo

Fig. 5. FE-SEM images of pure LDH (a and b) and organo-modified LDH (c and d).

Fig. adapted with permission from: Ref. [63].

Roman et al. used the anion exchange for intercalation of the Zn-Al-LDH with

different anionic drugs such as diclofenac, chloramphenicol, and ketoprofen at pH = 9

[64]. The XRD patterns revealed that the LDHs modified with ketoprofen and

diclofenac indicated higher crystallinity with the gallery distance of 21.97 and 23.35 Ao.

14
 Journal Pre-proof

Another research group [65] intercalated LDH with different organic linkages.

The d-spacing, molecular formula, and slight replacement of divalent cation by trivalent

cation in the surface of layer (x) for the intercalated LDH with organic segments

[synthesized LDH (cLDH1), commercial LDH (cLDH2), stearic acid intercalated LDH

(iLDH), and unmodified LDH (nLDH)] are shown in Table 1. As shown in Table 1, the

value of d-spacing for iLDH sample was increased, which indicated its micro-sized

composites compared to other nano-sized composites. Also, the higher d-spacing of

iLDH reduced its residue (%) at 900 oC in comparison with others.

of
ro
Table 1 Compositional data and formula for the LDH precursor and the modified
-p
derivative products. Table adapted with permission from: Ref. [65].
re
Sample Magnesium to aluminum mole X Apparent formula Residue (%) d-spacing,
ratio at 900 oC nm
lP

nLDH 2.92 0.26 [Mg0.74Al0.26(OH)2](CO3)0.13 55.89 0.76

iLDH 2.50 0.29 [Mg0.71Al0.29(OH)2](C18H35O2)0.14 29.36 4.90

cLDH1 2.94 0.25 [Mg0.74Al0.25(OH)2](CO3)0.13 54.48 0.76

na

cLDH2 2.07 0.30 [Mg0.70Al0.30(OH)2](CO3)0.15 55.40 0.76

ur

4.4. Hydrothermal method

Jo

In this method, autoclave with autogenous pressure is examined to prepare the

LDH sample. Also, high temperature (between 60 to 200 oC) is used to prepare LDH,

which this high temperature is known as a restriction of this method compared to the

coprecipitation method. This method is usually used for the fabrication of the LDHs

with large particle sizes and high crystalline structure [66]. Furthermore, the reaction

time and pH of solution are important parameters that can affect the LDH structure and

its interlayer space in this method [67, 68].

15
 Journal Pre-proof

Binder-free Co3O4@LDH core-shell nanostructured material was prepared

through the hydrothermal method, and its electrochemical performance was studied by

Li et al. [69]. The surface morphology of the Co3O4 and Co3O4@LDH materials

exhibited the growth of flower-like Co3O4 samples on the Ni surface, and after LDH

loading, the as-prepared sample exhibited the rough and bulky morphology. Also, the

high degree of specific capacitance, suitable rate capability, and cycling stability were

obtained for the Co3O4@LDHs with the molar ratio of 2 to 1.5 for the Co3O4 to LDH.

Also, Zhou et al. [70] synthesized NiV-LDH on the surface of Ni foam through

of
the hydrothermal method at 393 K. Then, the S2- was modified between the LDH sheets

ro
through the ion exchange way at 393 K (Fig. 6). An important advantage of this
-p
research was the Ni foam, which acts as a source of Ni for the LDH sample.
re
lP
na
ur

Fig. 6. Schematic illustration of the two-step strategy for preparing NiV-LDH and NiV-

S electrodes. Fig. adapted with permission from: Ref. [70].

Jo

In a research studied by Gholami et al. [71], the hydrothermal approach with a

temperature of 90 oC (24 h) was applied in order to biochar synthesized-LDH. The XRD

results showed the adsorption peaks matched with both pure Fe-Co-LDH and biochar

for the obtained biochar-LDH hybrid though the crystallinity and surface area of this

hybrid was decreased in comparison with the pure LDH.

Li et al. [72] used the hydrothermal method with high temperature to prepare

poly(ethylene glycol) (PEG) grafted Mg-Al LDH (PEG-haired LDH). Before PEG

16
 Journal Pre-proof

grafted, the TEM image of LDH showed the hexagonal shape with the particle size in

the range of 100-300 nm. But, the sulfate PEG modification changed the LDH shape to

pie-like disk [Fig. 7(A, B, C)]. This result was confirmed with the 3D pictures of SEM

images; the high disk-like samples were fenced by little soft coronas, which the prior is

related to the LDH particles, and second is related to the presence of PEG chains. Since

PEG is a harmless hydrophilic compound with high biocompatibility, thus, LDH

interacted with PEG molecules can be studied as an important model vehicle in bio-

delivery requests in future studies.

of
ro
-p
re
lP
na
ur
Jo

Fig. 7. TEM images (A-C) and SEM images (D-F) of sulfate PEG0.6k/LDH (A and D),

sulfate PEG2k/LDH (B and E), and sulfate PEG5k/LDH (C and F) samples after 72 h

reaction. Scale bar: 100 nm. Fig. adapted with permission from: Ref. [72].

4.5. Urea hydrolysis

In this method, because of great water solubility and easy hydrolysis of urea, it is

applied as a significant agent for the precipitation of metallic ions. This method is

usually applied for the synthesis of LDH having carbonated interlayer, and also to

17
 Journal Pre-proof

produce the highly crystalline LDH, the control of pH and temperature is very necessary

[35, 73]. The low amount of supersaturation during the urea process is increased the

importance of this method compared to the NaOH as a precipitating agent [74, 75].

Also, the produced LDHs through this method show higher crystallinity and distribution

size than the other reported methods. Urea hydrolysis is usually used for the preparation

of carbonated LDHs, which restricted the applications of this method. However, with

the precise control of pH, temperature, and with the presence of excess nitrate anions,

the LDH-nitrated can be fabricated [76, 77]. Wu et al. [78] applied the urea hydrolysis

of
for the synthesis of NiAl-LDH, and the prepared material was used for the synthesis of

ro
high efficient silver nanowire-LDH (Ag NW@NiAl LDH) hybrid. The general
-p
mechanism of urea hydrolysis to prepare of NiAl-LDH is as below (Equations 3-6):
re
NH2CONH2 → NH4+ + NCO- (3)

NCO- + 3H2O → HCO3- + NH4+ + OH- (4)

lP

HCO3- → CO32- + H+ (5)

na

6Ni2+ + 2Al3+ + 16OH- + CO32- + 4H2O → Ni6Al2(OH)16CO3.4H2O (6)

It shows that the produced CO32- in the final step interacts with Ni2+ and Al3+ to form
ur

carbonated LDH materials.

Jo

In another research, at first Zn-Al-LDH (Zn2+/Al3+ = 2) was prepared in the

presence of urea at pH = 8.5-9.0, and then sodium dodecyl sulfate (SDS) intercalated

LDH was prepared through anion exchange method [79]. Their results showed high

porosity and high surface area of the prepared SDS-LDH, which increased its ability to

remove different organic pollutants from wastewater [79, 80].

Liu et al. [81] used the different molar ratio of Zn/Al for the preparation of

LDHs through urea hydrolysis, and they observed that the crystallinity of formed LDHs

18
 Journal Pre-proof

was decreased with the enhancing of Zn/Al molar ratio. They showed that all LDHs

could be used as a valuable source to produce spinel.

Furthermore, in a research studied by Inayat et al. [35], urea was used for the

preparation of nitrated-ZnAl-LDH with the high crystallinity and plate-like shape

through the control of pH, reaction time, and temperature. As a matter of fact, the main

advantage of their research was owing to the NO3- between the layers, which increased

the anion exchange property of them.

of
4.6. Microwave method

ro
Microwave irradiation is used as a fascinating technique for synthesise and
-p
modification of LDH materials. This technique usually generates the homogeneous bulk
re
of samples, decreases the thermal slopes, and produces the normal heat, which improves

its importance compared to the high-pressure steel autoclaves in the hydrothermal

lP

method [82, 83]. The major advantage of microwave ovens is associated with an
na

extraordinary decrease in the time required to complete the reaction process compared

with other procedures [34]. Also, this technique improves the fast precipitation of LDH
ur

materials. One subject that restricts the use of microwave technology in comparison to
Jo

the coprecipitation method is due to simple and does not require specific experimental

devices for the coprecipitation method [34].

Fang et al. [84] applied the microwave technique to prepare of LDH/graphene

oxide (GO) hybrid (Fig. 8), which firstly GO materials were exfoliated in the deionized

water, and then the LDH samples were grown on their surface through heating,

refluxing, and centrifuging. The N2 adsorption-desorption results exhibited that the

specific surface area was increased for LDH/GO hybrid (40.8 m2 g−1) compared to the

pristine GO (7.7 m2 g−1) and LDH (29.6 m2 g−1).

19
 Journal Pre-proof

Fig. 8. Schematic illusions for the synthesis process of LDH/graphene oxide composite.

Fig. adapted with permission from: Ref. [84].

of
Recently, firstly MgAl-NO3-LDH (Mg2+/Al3+ = 2.5) was synthesized through a

ro
low-cost coprecipitation method, and after that, it was modified with two organic
-p
molecules, cholate and deoxycholate, through anion exchange method with the help of
re
microwave technique after 1, 2, and 3 h [85]. The observed results showed that 1 h was
lP

the best time to intercalate organic molecules into the layers with no cross-over. Thus,

they proposed this procedure as a timesaving and more expeditious method with high
na

efficiency compared to others.

ur

Also, Lonker et al. [86] synthesized graphene/LDH nano-hybrid through the

microwave technique with the urea hydrolysis reaction under hydrothermal conditions.
Jo

The TEM image of GO (Fig. 9a) sample showed the wavy and scrolled multilayer

sheets, but, for the GO/LDH hybrid (Fig. 9b) the round-shaped LDH platelets was

observed.

20
 Journal Pre-proof

of
Fig. 9. TEM micrographs of (a) GO, and (b) GO/Zn-Al LDH nano-hybrids. Fig. adapted

with permission from: Ref. [86].

ro
-p
re
In other research work, the microwave-assisted synthesis of high crystalline
lP

ZnNiAl-LDH as a simple and timesaving technique was studied [87]. They observed the

spherical-shaped LDH contains numerous agglomeration with considerable surface area

na

(52.3 m2 g-1) and pore diameter (16.8 nm).

Moreover, Zn-Co-LDH with the specific surface area of 116.4 m2 g-1 was
ur

produced using the microwave-assisted technique by Qiao et al. [88]. The AFM
Jo

observations indicated that the increase in the microwave reaction time from 5 to 20 min

was able to increase the crystalline size of LDHs.

4.7. Sol-gel method

Here, firstly, sol is formed with the hydrolysis of metallic precursor, and then a

gel is formed with its partial condensation [89]. Different compounds can be studied as

metallic precursors, including inorganic salts and metal-oxides, and the rate of

hydrolysis and condensation can affect the physical behaviors of the sol-gel prepared

21
 Journal Pre-proof

materials. The obtained LDHs with this method usually show the high specific surface

area, high purity, and high homogeneity [74, 89]. Also, some important advantages of

this method are high efficiency, low temperature, and simplicity [90].

Chubar et al. [91] used the sol-gel procedure with two forms of alkoxide and

alkoxide-free to fabricate LDH. The Mg-Al-CO3 LDH obtained with alkoxide-free route

revealed the reactive structure with lots of hydroxyl groups on the surface and mobile

interlayer ion. Moreover, the prepared LDH showed greater specific surface area (10-

25%) than other way like the coprecipitation method. Furthermore, sol-gel is known as

of
a cost-effective and environmentally-friendly method.

ro
Smalenskaite et al. [92] used two coprecipitation and sol-gel methods for the
-p
fabrication of cerium-substituted LDHs. The sol-gel procedure was examined with citric
re
acid and ethylene glycol at 80 oC for 1 h. They observed that the crystalline structure of

prepared LDH was increased with the sol-gel method. Also, according to the obtained
lP

data from lattice parameters, the value of cerium substituted was increased for sol-gel in
na

comparison with the coprecipitation method.

In another research work, Smalenskaite,s research group [90] used the sol-gel
ur

method (similar to the prior) to intercalate terephthalate anion into the LDH structure,
Jo

which modifying molecule influenced the luminescence behavior of LDH.

5. Applications of the modified LDHs

Because of the pointed features and facile synthesis, LDHs have significantly

interested in modern technology. Hence, in this section, we will critically review some

novel and important applications of modified LDHs in different fields.

5.1. Modified LDH/polymer nanocomposites (NCs)

22
 Journal Pre-proof

Currently, polymer NCs containing LDH nano-materials have provided a new

understanding of research to explore the outstanding potential applications of them.

With the incorporation of LDHs into the polymer chains, the optical, thermal,

mechanical, and chemical properties of both LDH and polymer chains are improved

[39, 43, 93]. For example, chiral diacid intercalated Mg/Al-CO32--LDH was examined

as organic-inorganic filler in the synthesis of NCs based on poly(amide imide) (PAI)

[94], and poly(vinyl alcohol) (PVA) [55]. The found results disclosed that the thermal

features of both polymer chains were increased with the increasing of the LDH amount.

of
A reason for selecting of Mg and Al as metallic cations in LDH structure was due to the

ro
metal hydroxide-like chemistry and clay-like layered crystalline construction of them.
-p
Also, the presence of chiral and biodegradable segments in the structure of PAI was a
re
prominent aspect of this research, which candidates the PAI as an appropriate

compound with high thermal properties in the industrial applications such as

lP

construction.
na

Zhang et al. [95] showed that the γ-(2,3-epoxypropoxy)-propyltrimethoxysilane

(KH560) modified LDH improved the thermal and rheological features of bitumen.
ur

They observed the positive effect of the KH560-LDH as a stable material to promote the
Jo

UV aging resistance of bitumen in comparison to the pure LDH. Accordingly, this paper

provides an important and critical effort, which can be extensively used in road

construction.

Zhang et al. [96] used ZIF-67, a kind of metal-organic framework (MOF), to form a

dual LDH hybrid through the connection of two different LDHs, NiCo-LDH and MgAl-

LDH, which can increase the dispersity of LDHs in epoxy resin. As TEM images show

(Fig. 10), the prepared dual LDH hybrid (MgAl@NiCo) indicated the smaller lamellar

size and higher dispersity in epoxy resin in compared to the MgAl-LDH with high

23
 Journal Pre-proof

aggregation degree. Furthermore, only 2.5 wt% of this hybrid increased the flame

retardancy of epoxy resin about 66.7%.

of
ro
-p
re
lP
na

Fig. 10. TEM and magnified TEM images of (a and b) epoxy resin/2.5% MgAl and (c

and d) epoxy resin/2.5% MgAl@NiCo. Fig. adapted with permission from: Ref. [96].
ur
Jo

Xie et al. [97] intercalated the LDH with lauryl phosphoric acid ester potassium, and

then the organic LDH (OLDH) with different percentages (0-6 wt%) was applied for the

preparation of polymeric NCs having linear low-density polyethylene (LLDPE). The

observed results showed that NC with 2 wt% of OLDH had the greatest physio-

chemical performance such as mechanical and gas barrier properties. Consequently,

owing to low-cost films, they can be used in agricultural plastics.

As previously mentioned, the effect of cardanol-BS modified LDH (m-LDH) nano-

hybrid on the thermal features of epoxy resins is studied by Wang et al. [49]. As can be

24
 Journal Pre-proof

seen in Fig. 11a, pure epoxy resin burns ferociously upon ignition with a sharp peak

heat release rate (PHRR) about 790 kW m-2, while this parameter is decreased for its

NCs, and epoxy resin/m-LDH 6 wt% shows the optimal PHRR value (about 304 kW m-
2
). Moreover, when the epoxy resin was composited with unmodified LDH, its flame

retardant property do not show any remarkable change (Fig. 11a). According to Fig.

11b, the epoxy resin containing the higher values of m-LDH shows the lower values of

the total heat release rate. Here, a significant aspect is the existence of cardinal-BS as a

bio-based modifying spacer, which was achieved from the renewable resource cashew

of
nut.

ro
-p
re
lP
na
ur
Jo

25
 Journal Pre-proof

Fig. 11. (a) Heat release rate (HRR) and (b) total heat release (THR) versus time curves

of epoxy resin (EP) and its flame retardant composites. Fig. adapted with permission

from: Ref. [49].

Also, the influence of 4,4-diaminostilbene-2,2-disulfonic acid (DDA) intercalated

Mg-Al-NO3--LDH on the non-isothermal crystallization kinetics of poly(ethylene

terephthalate) (PET) was studied by Cao et al. [98]. Their results indicated that the

addition of LDH-DDA nano-materials acted as a nucleating agent and enhanced the

of
non-isothermal crystallization process of pristine PET. Similarly, the prepared PET NCs

ro
containing the LDH-DDA displayed a dramatically upgraded crystallization rate
-p
compared to pristine PET.
re
A research study investigated the immobilization of adamantine on the surface of

Tb3+-doped-LDH to prepare a polymeric composite having β-cyclodextrin with

lP

hyperbranched polyglycerols [99]. The obtained composite indicated good water

na

dispersibility with high fluorescence behavior. Also, its toxicity was very low, which

proved its application to be considered in bio-medical areas.

ur

In a research by Martos et al. [100], the conductive property of a new class of

Jo

organic-inorganic NC membranes based on heptamolibdate modified Zn-Al-LDH and

sulfonated polysulfone was studied. The results displayed that the heptamolibdate-

modified LDH was slightly increased the conductive property of sulfonated

polysulfone, which improved its potential to be used in proton exchange membranes

and fuel cells. In fact, the critical advantage of this research was due to the examined

LDHs to improve the conductive behavior of the polymeric matrix in comparison with

the traditional materials such as TiO2.

26
 Journal Pre-proof

Also, spirocyclic pentaerythritol bisphosphorate disphosphoryl chlorine intercalated

LDH (SPDP-LDH) was considered as organic-inorganic filler for the preparation of

unsaturated polyester resin NCs [101]. The TGA and stress-strain results exposed higher

thermal and mechanical behaviours of polyester resin NCs than its pure matrix,

respectively. This paper focused on the spirocyclic phosphorus as green materials with

high charring capacity, which can efficiently decrease the smoke and harmful gas

substances compared to the halogenated flame retardant during the burning process.

Another research group [102] focused on the sodium dodecyl benzene sulfonate

of
(SDBS) intercalated LDHs (MgAl, CoAl, NiAl, and ZnAl) to improve the flame

ro
retardant feature of polystyrene (PS) NCs. Smoke suppression results indicated a
-p
decrease in the peak values for PS with LDH nano-layers, which confirmed a great
re
degree of flame retardancy for these NCs. In addition, Fig. 12 shows that after cone

calorimeter tests, the residual char of all NCs was increased [residue (%); pure PS =
lP

0.58, PS/MgAl-SDBS-LDHs = 2.36, PS/CoAl-SDBS-LDHs = 1.47, PS/NiAl-SDBS-

na

LDHs = 1.85, and PS/ZnAl-SDBS-LDHs = 1.77]. Here, authors have focused on the

green and halogen-free LDH compounds, which do not have any harmful influences on
ur

the atmosphere.
Jo

27
 Journal Pre-proof

Fig. 12. Residues at the end of cone calorimeter tests (a) PS, (b) PS/MgAl, (c) PS/CoAl,

(d) PS/NiAl, and (e) PS/ZnAl-LDHs NCs. Fig. adapted with permission from: Ref.

[102].

Kalali et al. [103] observed that the Fe3O4 nano-sphere@MgAl-LDH intercalated

with bio-molecules not only enhanced the flame retardant property of epoxy resin NCs

but also improved their thermal conductivity. As a matter of fact, this finding

demonstrated the applications of the environmentally-friendly and non-toxic LDH

of
materials for the development of anti-flammability of the epoxy resin matrix compared

ro
to the traditional halogenated materials. -p
Zhang et al. [104] used the sulfamic acid intercalated LDH (SA-LDH) hybridized
re
with aluminum phosphinate (AlPi) to enhance the flame retardancy, stability, and

mechanical strength of polyamide 11. The miscibility of polyamide 11 with AlPi

lP

improved its mechanical strength, flame retardancy, and thermal feature.

na

Organophosphorus compounds have a critical role in this research because the obtained

phosphoric acid and polyphosphates materials during the reaction produce the viscous
ur

char layers in the polymeric matrix and protect it to further combustion.

Jo

Hu and Chen [105] reported a novel type of polymeric NC hydrogel based on

polyacrylamide and isethionate intercalated LDH. This kind of material revealed

ultrahigh tensibility and a porous structure with high mechanical properties.

In other research, Labuschagne et al. [106] examined the stearic acid molecule

coated LDH as a good heat stabilizer for the fabrication of poly(vinyl chloride) (PVC)

NCs. The effect of the different LDHs on the thermomat stability times of the flexible

PVC indicated the greatest performance of dynamic heat stability for conventional

28
 Journal Pre-proof

MgAl-LDH, although the replacement of metallic cations altered the content of dynamic

heat stability (Fig. 13).

of
ro
-p
re
Fig. 13. Static and dynamic heat stability times measured at 200 oC using the
lP

torquerheometer technique (Rheomix); following the development of color with heating

time (Metrastat), and tracking the evolution of hydrochloric acid (Thermomat induction
na

and stability times). Fig. adapted with permission from: Ref. [106].
ur

Also, two anionic phosphorus materials (HPO42− and HDEHP−) were effectively
Jo

intercalated into the Mg/Al-CO3-LDH, and these materials were used for the fabrication

of flexible and elastic polyurethane NC foams [107]. The thermal behavior of the

prepared NCs was improved, and the results showed the high value of residue compared

to the pristine matrix.

5.2. Antibacterial application

Recently, both modified LDHs and hybridized LDHs with silver nanoparticles

(NPs) have been examined as antibacterial agents against different bacteria. This is

29
 Journal Pre-proof

associated with many factors such as the uniform dispersion of the Ag NPs on the

surface of LDHs, decreasing of Ag bandgap, positive interactions of LDHs with Ag

NPs, and positive interactions of LDHs with bacteria cell wall [108-110]. In the last

decade, many studies have reported the application of modified LDHs to be considered

in antibacterial areas.

Merchan et al. [111] synthesized CO3-Zn2Al and Pd(II)-5,10,15,20-tetrakis(4-

carboxyphenyl) porphyrin (PdTPPC)-Zn2Al LDH fillers, and then examined the photo-

bacterial features of the polyurethane NC films containing the PdTPPC-Zn2Al. The

of
results of the photo-physical behaviours displayed the PdTPPC with more stability in

ro
the with LDH material under chemical conditions. Also, when the antimicrobial test of
-p
these PdTPPC-Zn2Al/polyurethane NCs was studied, they were able to stop the growth
re
of Staphylococcus Aureus (S. Aureus) without the release of PdTPPC biocide from the

NC film.
lP

In a novel study, three different kinds of modified-LDH with organic molecules

na

[poly dopamine, tannic acid-Fe(III), and poly(vinyl pyrrolidone)] were used for

reduction of [Ag(NH3)2]+, and the Ag NPs loaded on the surface of modified-LDH

ur

hybrids with high dispersity were prepared [112]. All modified-LDHs showed a high
Jo

tendency to reduce [Ag(NH3)2]+ salt, and also the antibacterial property of all hybrids

was very remarkable against S. Aureus and Escherichia Coli (E. Coli) bacteria.

Mishra et al. [113] studied the antibacterial application of Ag incorporated Zn-Al

LDHs. The results of the antibacterial experiment indicated that both pure LDH and Ag-

LDH were more stable in the acidic situation with the great antibacterial performance

against both S. Aureus and E. Coli (Fig. 14). Table 2 summarizes the results of the

antibacterial test for the pure LDH, Ag-LDH, and Ag-LDH calcinated at 800 oC.

Similarly, Table 3 does not show any obvious changes in the antibacterial activity of

30
 Journal Pre-proof

samples after 2 days, which confirms the great potential of these materials in the field of

ceramics.

of
ro
-p
Fig. 14. Antibacterial test (disc method): (a) S. Aureus, (b) E. Coli (1) Blank LDH, (2)

Ag-LDH-800 oC, (3) Ag-LDH aged. Fig. adapted with permission from: Ref. [113].
re

Table 2 Zone size of diffusion susceptibility disc. Table adapted with permission from:
lP

Ref. [113].
na

Sample name Activity and zone size (mm)

E. Coli S. Aureus
ur

Blank LDH Inactive Inactive

Ag-LDH aged 8 13
Jo

Ag-LDH-800 oC 15 18

Table 3 Zone size reduction up to day 7 for Ag-LDH calcinated at 800 oC. Table

adapted with permission from: Ref. [113].

Sample name Activity and zone size (mm)

E. Coli S. Aureus

Day 1 15 18

Day 3 15 18

31
 Journal Pre-proof

Day 5 14 17.5

Day 7 13 17

El-Shahawy,s research group [114] focused on the antibacterial property of

doxycycline modified LDH and compared its performance with other materials such as

the pure LDH, cobalt ferrite NPs, and chitosan NC containing the cobalt ferrite NPs.

Their results revealed while the inhibition of S. Aureus was low with pure LDH and

pure cobalt ferrite NPs but the doxycycline modified LDH and cobalt ferrite-chitosan

of
NC as incredibly decreased the bacteria growth.

ro
Chen et al. [115] observed that the Ag decorated LDH was very durable with
-p
excellent antimicrobial application against Gram-negative [E. Coli and Pseudomonas
re
aeruginosa (P. Aeruginosa)] and Gram-positive [Bacillus subtilis (B. Subtilis) and S.

Aureus] bacterial. Also, about 100% of bacteria were killed only after 3 h (Fig. 15).
lP

Similarly, they observed that more than 90% of bacteria were killed after four steps of
na

recycling.
ur
Jo

32
 Journal Pre-proof

Fig. 15. The biocidal efficacy of the Ag-LDH 3 h coating on the glass substrate against

E. Coli, P. Aeruginosa, S. Aureus, and B. Subtilis. Fig. adapted with permission from:

Ref. [115].

Another research group [116] intercalated the carboxymethyl cellulose (CMC) in the

interlayer of LDH and investigated the antibacterial potential of Ag/CMC-LDH NCs

against S. Aureus and E. Coli bacteria. They observed the great antibacterial

performance of Ag/CMC-LDH NCs for both bacteria, and its antibacterial activity was

of
stable for more than one month.

ro
Recently, Allou et al. [117] modified the LDH with norfloxacin (NOR), and the NC
-p
hybrids having citric acid crosslinked CMC and LDH-NOR were synthesized on the
re
surface of functionalized carbon (AC). The results of the disc diffusion test showed that

the examined samples could inhibit the growth of all bacteria, and their antibacterial
lP

activity was different by different concentrations of CMC (Fig. 16).

na
ur
Jo

33
 Journal Pre-proof

of
ro
-p
re

Fig. 16. Antimicrobial studies against (a) S. Aureus, (b) P. Aeruginosa, (c) B. Subtilis
lP

and (d) E. Coli of: (1) C1 (0.25 g CMC, 50 mg citric acid, and 50 mg AC-LDH-NOR),
na

(2) C2 (0.50 g CMC, 50 mg citric acid, and 50 mg AC-LDH-NOR), (3) C3 (1.0 g CMC,

50 mg citric acid, and 50 mg AC-LDH-NOR), and (4) control antibiotic (NOR). Fig.
ur

adapted with permission from: Ref. [117].

Jo

Also, Xiao et al. [118] doped the Ruthenium complex as a photodynamic sensitizer

and the Ag NPs as antimicrobial agents in the structure of LDH and the produced Ag-

Ru/LDH hybrid was applied for inhibition of E. Coli and S. Aureus bacteria growth.

Their results demonstrated an increment in the antibacterial activity of the Ag-Ru/LDH

compared to the Ru/LDH and pure LDH under illumination. Furthermore, they

observed an enhancement in the antibacterial activity of the Ag-Ru/LDH with the

increase in sample concentration.

34
 Journal Pre-proof

Furthermore, the possible interactions in which the Ag NPs loaded on vitamin B9

(VB9)-modified-LDH (Ag@VB9-LDH) can trap the bacteria structure are discussed by

Mallakpour et al. [119]. They said that the Ag@VB9-LDH could interact with bacteria

cell wall through H-bonds of VB9 functional groups with –SH functional groups of

bacteria, and electrostatic interactions of positive charges of Ag NPs and LDH layers

with negative charges of the bacteria cell wall (Fig. 17). Additionally, with this hybrid,

the ability of chitosan to prohibit the growth of E. Coli and S. Aureus bacteria was

increased.

of
ro
-p
re
lP
na
ur

Fig. 17. Schematic inhibition and degradation of the cell wall of bacteria with
Jo

Ag@VB9-LDH. Fig. adapted with permission from: Ref. [119].

5.3. Removal of pollutants

In the last decade, the applications of modified LDHs as recyclable adsorbents for

the uptake of poisonous metallic ions, organic pollutants, CO2, and so on are increased

in both academia and technological studies. Since LDHs have cationic layers, thus, they

can easily interact with anionic molecules [120]. Also, the anionic exchange is a good

parameter that effects the LDH adsorption capacity; due to tunable property of layers,

poisonous anionic molecules can exchange with LDH interlayer molecules [121].

35
 Journal Pre-proof

Furthermore, lots of hydroxyl groups and organic spacers of modified-LDH are other

factors to increase LDH interactions with pollutants [122].

Asiabi et al. [123] intercalated six different organic anions such as diphenylamine-4-

sulfonate (DPA), dodecyl sulfonate (DS), pentansulfonate (PS), terephthalate (TA),

fumarate (FA) and 2-ethylhexyl hydrogenphosphate (EHP) into the interlayer of LDHs

and studied the removal of different cationic metals such as Cd(II), Pb(II), Cu(II), and

Zn(II) ions from water test solution. They observed that these anions could affect the

adsorption process in the order of DPA> DS> PS> TA> FA> DEHP. Also, the DPA-

of
LDH could to uptake the poisonous cations in the order of Zn(II)< Cu(II)<<< Cd(II)<

ro
Pb(II) ions. -p
A research work studied the effect of organic modified-LDHs on the adsorption of
re
CO2 [124]. The results indicated that the number of carbon of modifying agent was an

important parameter that affects the adsorption of CO2; for the modifying agent with
lP

carbons more than 10, its CO2 adsorption was incredibly increased.
na

Another research work focused on the LDH intercalated with L-cysteine (Cys-LDH)

as a fascinating adsorbent for the elimination of U(VI) ion from the aqueous solution
ur

(adsorption capacity = 211.58 mg g-1) [125]. The schematic uptake of U(VI) ion through
Jo

Cys-LDH is shown in Fig. 18, which most interactions are (1) attractions between

positive-charged layers and UO22- (electrostatic forces), and (2) created stable

complexes through the active sites of Cys-LDH and U(VI) ions. This research focused

on the low-cost adsorbent with a higher maximum adsorption capacity of the U(VI) ions

compared to similar adsorbents [126, 127]. The functional groups of L-cysteine (NH2,

COOH, and SH) increased its effective interactions with U(VI) ions.

36
 Journal Pre-proof

of
Fig. 18. Schematic of the adsorption mechanism of U(VI) ion on Cys-LDH. Fig.

ro
adapted with permission from: Ref. [125]. -p
re
Li et al. [128] prepared the Rhamnolipid-LDH NCs to uptake both Cu(II) ion and p-
lP

cresol from wastewater. The adsorption results exhibited a higher adsorption capacity of

these NCs in comparison to LDH for p-cresol/Cu(II) ions.

na

Also, Mallakpour and Hatami [129] showed the merit of PVC NCs having

intercalated LDH with bio-organic molecules as an affordable adsorbent for the

ur

elimination of Cd(II) ion from wastewater. The modified LDH/PVC NCs revealed
Jo

higher maximum adsorption capacity than the pure LDH and modified LDH. The major

advantage of this research was owing to the preparation of NC film with easy separation

from aqueous solution. Furthermore, in this paper PVC NC with only a low percentage

of modified LDH was able to separate the cadmium metal from wastewater, which

approves the affordability of this work. Since the polar functional groups of PVC are

not high, thus, it is a good idea to apply other polymeric matrices with higher polar

functional groups in future studies.

37
 Journal Pre-proof

Also, a research work showed that the LDHs were incredibly able to promote the

adsorption percentage of maifanite to uptake Cd(II) ion [130]. The results revealed that

the adsorption efficiency was improved from 86.0% for pure maifanite to 97.54% and

97.66 for maifanite composited with MgFe and MgAl-LDH, respectively.

In another study, toxic dyes were successfully eliminated from aqueous solutions

through Zwitterionic histidine LDH (His-LDH) nano-hybrids (99.98% congo red,

99.78% sunset yellow FCF, and 99.98% indigo carmine) [131]. This research

considered the histidine amino acid with both anionic and cationic functional groups for

of
modification of LDH, which can increase its interactions with anionic and cationic dyes.

ro
Moreover, the removal efficiency of this adsorbent was very remarkable after 12 runs
-p
(Fig. 19). Therefore, it has the potential to be used in modern industrial areas.
re
lP
na
ur
Jo

Fig. 19. Effect of recycling His-LDH on Congo red (CR), indigo carmine (IC), and

sunset yellow FCF (SY) uptake. Fig. adapted with permission from: Ref. [131].

Also, when LDH was intercalated with dodecylsulfate, it could considerably

eliminate different toxic dyes such as congo red, methyl orange, and brilliant green with

high adsorption capacities of 149.13, 114.19, and 87.0 mg g-1, respectively [80]. This

38
 Journal Pre-proof

result was owing to the hydrophobic and hydrophilic functional groups of the modifying

agents, which can easily connect these dyes with LDH structure through active sites.

Furthermore, with the modification of LDH, its surface area was increased.

Sidek et al. [132] hybridized the LDHs with the MOF materials to improve their

hydrostability. The self-assembly between copper benzene tricarboxylate (Cu-BTC)

MOF and LDH layers reduced the particle size of spherical Cu-BTC and also increased

the surface area of this hybrid, which increased its efficiency to eliminate Cu-BTC in

water compared to pristine samples.

of
Dinari et al. [133] indicated that the adsorption of Cd(II) ions through ethylene

ro
diamine tetraacetic acid (EDTA) intercalated-LDH-PVA NC was affected with pH,
-p
concentrations of both adsorbent and adsorbate, reaction time, and temperature. Their
re
results confirmed the notable adsorption capacity of this adsorbent fitted with Langmuir

isotherm, proving the mono-layer nature of the adsorption process.

lP

Duan et al. [134] eliminated As(V) ions from glucose solution through calcinated
na

starch intercalated-Mg/Al-LDH (C-S-LDH) hybrid as an effective bioactive agent with

higher maximum adsorption value (36%) in comparison to calcinated pure LDH.

ur

A research group focused on the LDH intercalated with 2-hydroxyethylammonium

Jo

acetate hydroxylammonium ionic liquids (ILs) for adsorption of negative charged dye

orange 5 with greater adsorption capacity (300.9 mg g-1) than the pure LDH (53.9 mg g-
1
) [135]. An important key in this research was associated with the ILs as a good

modifying molecule, which has exceptional features such as small vapor pressures,

adequate stability, and prominent solubility.

Also, Mallakpour and Behranvand [136] applied the recycled PET/LDH-

multiwalled carbon nanotubes (MWNT) NCs with a high surface area to eliminate

Cd(II) ion from water test solution. They compared the highest maximum adsorption

39
 Journal Pre-proof

capacity of this NC (38.91 mg g-1) with the other similar adsorbents such as pure

bentonite (10.47 mg g-1), pure recycled PET (11.35 mg g-1), and pure CNT (14.45 mg g-
1
). Although the MWNT is so expensive, applying the ultrasonic irradiation as a green,

simple, and fast technique for the synthesis of modified LDH, fabrication of

MWNT/LDH-PET NC, and recycling of plastic solid is very noticeable and economical,

which can be helpful to the management of waste pollutants.

Zouai’s research group [137] showed that the Rhamnolipid (RL) intercalated LDH

decreased the surface area and increased the hydrophobicity behaviours of this material,

of
which these features increased the merit of this sample to eliminate p-cresol in water

ro
solution. -p
Recently, ultrasonic-assisted PVA NC film containing modified-LDH hybridized
re
with Fe3O4 as significantly was able to absorb methyl orange dye (about 94%)

compared to pure LDH (about 77%) [138]. As Fig. 20 shows, with the bio-organic
lP

diacid modification, the interlayer space of LDH is increased, which could decrease the
na

layers agglomeration and improve their interactions with the PVA matrix. Thus, methyl

orange as remarkably was absorbed on the surface of NC film and separated from the
ur

water solution.
Jo

40
 Journal Pre-proof

of
ro
-p
re
lP
na

Fig. 20. Schematic intercalation of organic diacid molecule in the LDH structure and

the calculated size of d-spacing. Fig. adapted with permission from: Ref. [138].
ur
Jo

Wang et al. [139] used the 3D sulfide segments to intercalate the LDH sample

and removed the various heavy metals as selectivity in the order of Pb(II)> Cu(II)≥

Zn(II)> Cd(II)> Mn(II) ions. Fig. 21 shows the schematic intercalation of LDH with

MoS42- and its SEM images. As can be seen, the obtained sample shows a flower-like

structure with high porosity, which increased the adsorption of heavy metals in these

pores.

41
 Journal Pre-proof

of
ro
Fig. 21. Synthesis schematic of the flower-like hierarchical NFL-S microstructure and

SEM images of the NFL-based composites with the addition of varying amounts of
-p
(NH4)2MoS4. Fig. adapted with permission from: Ref. [139].
re
lP

Another research work investigated the bamboo biomass for loading on the

surface of LDH modified with EDTA and studied the uptake of Cr(VI) ion from
na

wastewater [140]. Its results revealed the great adsorption capacity of this hybrid (38.0
ur

mg g-1) to remove Cr(VI) ion fitted with both Langmuir and Freundlich models. A key

point of this research was to interactions of Cr(VI) ions with EDTA molecules
Jo

modified-LDH, which improved the efficiency of this adsorbent.

Here, we briefly summarize the most reported researches associated with the

application of modified-LDHs for the removal of pollutants, and the maximum

adsorption capacity and probable mechanism are discussed (Table 4).

42
 Journal Pre-proof

Table 4 Summarized application of modified LDH for the removal of pollutants.

LDH adsorbent Pollutant Qm (mg g-1) Probable mechanism Ref.

LDH-dodecylsulfate Methyl 114.19 Hydrophobic and hydrophilic functional [80]

orange groups of adsorbent and their interactions

with methyl orange

Cys-LDH U(VI) 211.58 Electrostatic forces, and stable complexes [125]

through the active sites of Cys-LDH and

U(VI) ion

of
Rhamnolipid-LDH Cu(II) 116.14 Complexation of Cu2+ with Rhamnolipid [128]

ro
anions

Rhamnolipid-LDH p-cresol 37.63

-p
Hydrophobic interactions [128]
re

LDH/PVC Cd(II) 31.51 Electrostatic forces, hydrogen bonding, and [129]

lP

complexation of LDH/PVC and Cd(II)

na

His-LDH Congo red 1112.0 Electrostatic interactions, π-π, and H- [131]

ur

bonding interactions of His-LDH and

congo red dyes

Jo

EDTA-LDH/PVA Cd(II) 9.54 Surface complexation of EDTA-LDH and [133]

Cd(II)

LDH-ILs Reactive 300.91 Van der Waals interactions and ion [135]

orange 5 exchange behavior of adsorbent and

adsorbate

LDH-EDTA Cr(VI) 38.0 Anion exchange [140]

5.4. Anti-corrosion application

43
 Journal Pre-proof

Modified LDHs have been successfully applied in order to cover of alloy materials.

With LDH materials with low solubility, the resistance of alloy materials against the

external agent such as O2 and H2SO4 is increased, which promotes their applications in

the industrial fields. For example, the EDTA intercalated Zn-Al-Cl LDH is used as an

anti-corrosion agent in order to cover of aluminum alloy 2024 [141]. Because of the

host-guest structure of LDH, the intercalated EDTA molecule was released, interacted

with metallic alloy, covered its surface, and enhanced its anti-corrosion behavior.

Another important option in this research can be due to the presence of Zn2+ instead of

of
Mg2+ in the LDH sheets, due to the role of Zn2+-based layers, which decreases anodic

ro
metal dissolution [142]. -p
In a research studied by Li et al. [143] the multifunctional behaviors of Li-Al-LDH
re
modified with 2-guanidinosuccinic acid were observed. They resulted that the obtained

film not only increased the corrosion resistance of A6N01-T5 Al alloy but also inhibited
lP

the growth of bacteria and indicated the great self-repairing property.

na

Mei et al. [144] showed that aminobenzoate intercalated LDH was able to increase

the corrosion resistance of the epoxy coating. As Fig. 22 shows, when the concentration
ur

of modified-LDH was 0.5 wt%, the highest value of corrosion resistance was observed,
Jo

and for modified-LDH with a higher concentration (2 wt%), the lowest corrosion

resistance was observed. These results were due to the lower time for corrosion

initiation at higher concentrations.

44
 Journal Pre-proof

of
ro
Fig. 22. Open-circuit potential evolutions of the steel specimens with the epoxy coating
-p
containing MgAl-aminobenzoate LDH. Fig. adapted with permission from: Ref. [144].
re

Yao et al. [145] coated LDH modified with methyltrimethoxysilane (MTMS) and
lP

cerium nitrate on the surface of the AZ31 magnesium alloy. The MTMS molecules
na

increased the adhesion between LDH and CeO2 through Si-O-Si and Si-O-Mg

interactions. Also, the maximum corrosion resistance was produced with 10−3 mol L-1 of
ur

cerium nitrate, and after this concentration, the coating process was not valuable.
Jo

In other research work [146], polylactic acid (PLA) was covered on the outer

surface of AZ31-LDH nanostructure plates to enhance their corrosion resistance. The

XRD results exhibited clear peaks related to the Mg(OH)2 on the coated models, which

confirmed that the corrosion had occurred on the sample during the coating method at

high temperature and high pressure. Also, the observed results indicated a strong

adhesion of thick PLA coating with the porous outer layer of the ZnAl-LDH, and the

PLA coating hindered the penetration of destructive ions in order to deliver longer

protection. As a matter of fact, the proper corrosion protection of PLA coated LDH

45
 Journal Pre-proof

compared to the other protective coatings can be due to their barrier function, ion-

exchange, and self-healing capacity. One remarkable disadvantage of AZ31 is its high

corrosion capacity, which restricted its usage on a massive scale. Here, provided a

critical procedure to develop the corrosion resistance of magnesium alloy; therefore, the

produced compounds can apply as an advantageous and critical selection in automobile,

aerospace, and electronics.

Also, the photocathodic protection of 304 stainless steel through ZnFeAl-LDH

composited with TiO2 NPs was studied by Wang et al. [147]. The X-ray photoelectron

of
spectroscopy (XPS) results showed that the 304 stainless steel received a large number

ro
of electrons from ZnFeAl-LDHs/TiO2, and photocathodic protection was improved in
-p
compared with pure TiO2.
re
Furthermore, the effect of modification of LDH with disodium vanillin L-aspartic

acid (VLDH) on the corrosion resistance of A6N01-T5 Al alloy was examined by Lin et
lP

al. [148]. The schematic coating of A6N01-T5 Al alloy with VLDH in one step at low
na

temperature and 20 min is shown in Fig. 23. Their results confirmed the positive role of

the modifying agent on the anti-corrosion performance of LDH, and it increased the
ur

corrosion resistance of this material compared to the un-modified sample.

Jo

46
 Journal Pre-proof

of
ro
-p
re
lP

Fig. 23. Preparation route of the VLDH coating on the Al alloy. Fig. adapted with
na

permission from: Ref. [148].

ur

Tang et al. [149] observed that with the different interlayer anions of LDH, its
Jo

corrosion resistance against AZ31 Mg alloys is different. The LDH anion exchange

behavior was an important factor that affected its anti-corrosion performance. Hence, it

showed the corrosion resistance in the order of VO43−> MoO42−> PO43−> Cl-> NO3−.

5.5. Drug delivery application

LDH materials due to the nanostructure layers, low toxicity, high ion exchange

activity, high surface area, and pH-dependent solubility are applied in the drug delivery

systems. These materials can protect drugs against external agents such as sunlight, UV

47
 Journal Pre-proof

light, acidic and basic condition, temperature, etc. [150, 151]. One disadvantage related

to the LDH drug delivery system is due to the unstable nature of LDH in the acidic pH,

which causes the release of drug with high speed in the stomach condition. Hence,

recently with coating of LDH-drug with other materials such as biodegradable

polymers, its drug delivery performance is promoted [152, 153].

For example, Valarezo et al. [154] positively encapsulated the amoxicillin (AMOX)

intercalated LDH at various contents into the poly(ε-caprolactone) (PCL). The results of

release curves showed a controlling release of the AMOX for LDH-AMOX compared

of
to the pure AMOX. Accordingly, it can be said that the LDHs are helpful nano-

ro
crystalline materials, which can be studied in the biomedical fields like dental
-p
management and/or skin contamination. The advantages of LDHs in comparison with
re
the traditional methods such as encapsulate drugs into the fiber matrix are their higher

biocompatibility and lower structural stability in the selected conditions [155, 156].
lP

Mallakpour and Hatami [157] considered the effect of chitosan with 10 and 20 wt%
na

on the release of folic acid intercalated-LDH prepared with the ultrasonic-assisted

methods. They resulted that the higher concentration of chitosan delayed the folic acid
ur

release in the stomach (pH = 1.2) and promoted its release in intestine conditions (pH =
Jo

6.8 and 7.4).

In other research, Gao et al. [48] indicated that the Ca/Al-LDH reduced the release

of VC to 80% in comparison with 100% release of the pure VC at phosphate buffer with

pH = 7.4 (Fig. 24). This feature was corresponding to the durable host-guest contacts

such as hydrogen bonding and electrostatic interactions in the LDH-VC structure. The

presence of Ca2+ as metallic cation for the fabrication of the LDH layers is very

significant because the Ca/Al LDH is very biocompatible and exactly does not show

any serious cytotoxic effect for the body of vertebrate and invertebrate.

48
 Journal Pre-proof

of
Fig. 24. The obtained results for released drugs at phosphate buffers at pH 7.4. Empty

ro
squares: pure VC; solid circles: physical mixture (VC + Ca2Al-NO3); and solid
-p
triangles: Ca2Al-VC. Fig. adapted with permission from: Ref. [48].
re
lP

Also, Roman et al. [158] used dexketoprofen and aceclofenac as two common non-

steroidal drugs for modification of two various nanostructured matrices; LDH and
na

mesoporous silica (SBA-15). Their result revealed the role of both LDH and SBA-15 on

the controlled release of drugs, and the release rate was greater for the LDH in
ur

comparison to SBA-15; owing to the LDH anion exchange behavior.

Jo

Rojas et al. [159] reported that ibuprofen, naproxen, and ketoprofen intercalated

LDH improved the solubility of acid media, and these correlations were useful to

calculate and optimize the behavior of drug delivery systems.

In another study, a hybrid of Fe3O4 interacted with L-Dopa intercalated LDH with

an average size of 120 nm was prepared, and the in vitro drug release test showed about

53.8% of drug was released at low pH [160]. Furthermore, the in vivo test indicated that

the higher anticancer property of this hybrid against Mel-Rm Cells Melanoma was

observed with lower concentration of L-Dopa.

49
 Journal Pre-proof

Ferulic acid as a common organic drug was used for intercalation of MgAl-CO3-

LDHs with three various synthesis methods; ion-exchange, rehydration, and exfoliation-

reassembly [161]. The results of the ferulic acid release rate indicated that the

preparation method was a major factor in its release rate.

Moreover, the release of VC intercalated LDHs (Mg3Al-VC and Mg3Fe-VC LDHs)

in both aqueous/CO32– solutions and deionized water was studied by Gao et al. [162].

The Mg3Al-VC LDH system revealed the valuable controlled release of VC compared

to the Mg3Fe-VC LDH in both solutions. The fundamental effect of LDH as a matrix for

of
VC was due to the promoting of VC stability against air, water, and other conditions.

ro
Thus, it postponed the release speed of VC, and it was a good point for the body, which
-p
needs only a low value of VC. A distinct disadvantage of this research is due to the
re
unknown percentages of VC, which firstly intercalated and subsequently released in the

LDH matrix.
lP

A research studied by Li et al. [163] used a stretchable double-carrier system

na

containing polyurethane and PVA to delay the release of Quinolone antibiotics enoxacin

in LDH materials. Thus, this finding confirmed that the obtained hydrogel was able to
ur

be used in wound healing fields.

Jo

Barkhordari and Yadollahi [164] studied the in vitro drug release behavior of LDH

intercalated with cephalexin (CPX) crosslinked by CMC NCs. The gained data showed

high protection against drug release for CMC-LDH-CPX NC in comparison to the

LDH-CPX sample at stomach pH and also better-organized release in the intestinal

situations was observed (Fig. 25).

50
 Journal Pre-proof

of
ro
Fig. 25. Drug release behavior of LDH-CPX and CMC/LDH-CPX NC bead in
-p
conditions that simulate the gastrointestinal tract passage (pH and time). Fig. adapted
re
with permission from: Ref. [164].
lP

Also, as reported in previous sections, Liu et al. [57] observed the anti-cancer
na

outcome and controlled release speed of MTX in ultrasonic-assisted LDH-MTX. They

pointed out the effect of LDH, which do not show any dangerous influence in the
ur

direction of cancer cells and also it can be simply suppressed cancer cells from testing
Jo

solution.

Zuo et al. [165] used a present strategy and superficial method for surface

modification of LDH compound by angiopep-2 (Ang2) and rabies virus glycoprotein

(RVG) peptide as two targeting ligands through hydrothermal treatment at 100°C. High

selectivity and effective therapeutic behaviours of ligand-modified LDH for brain

tumors were observed in comparison with the unmodified LDH [165].

Also, Serjio et al. [166] studied the drug delivery behavior of ZnAl-LDH

intercalated with fenoprofen as a drug carrier. This research proposed the usage of

51
 Journal Pre-proof

LDHs as significant bio-safe materials to enhance the targeting release of NSAID drugs

[166].

5.6. Catalytic application

In many studies, LDHs have been considered as a catalyst and/or a catalyst

supporter; owing to the low-cost, biocompatibility, biodegradability, simple synthesis,

simple separation, and non-toxic properties of them [167, 168]. The key advantages of

LDH-catalyst are due to the fast process, small pollution and waste, and catalyst is

of
recoverable. Also, in some researches, with LDH-catalyst, the reaction takes place at

ro
lower temperatures, and its efficiency is increased [168, 169]. Now, some important
-p
examples of the application of LDHs as catalyst samples are expressed.
re
Sahoo and Parida [170] applied Pd(II)-LDH as a heterogeneous catalyst in order to

oxidation of primary alcohol (Scheme 1). They observed efficient oxidation of primary
lP

alcohol and the conversion rate was increased with time up to 6 h (Fig. 26). Also,
na

separation of the catalyst was very easy, and it was recycled multiple times with high

activity and selectivity (Table 5). The reaction was done in water as a green solvent and
ur

O2 as an oxidant without leaching of Pd species. Moreover, the reaction took place at

Jo

low temperatures.

52
 Journal Pre-proof

Fig. 26. Effect of time on oxidation of benzyl alcohol. Fig. adapted with permission

from: Ref. [170].

O
LDH/Pd(II)
R OH Mol.O2, Pyridine
R H
Water,65oC,6h

Scheme 1. Catalytic reaction pathway. Scheme adapted with permission from: Ref.

[170].

Table 5 Recyclability test up to four cycles. Table adapted with permission from: Ref.

of
[170].

ro
No. of cycle Conversion (%) Selectivity (%)

Fresh 94
-p 100

2 93 100
re
2 93 100
lP

3 91 100

4 88 100
na
ur

Jia et al. [171] applied a bifunctional hetero-catalyst based on NiFe-LDH and

defective graphene (DG) as an effective compound in order to overall water splitting.

Jo

Their results revealed high hydrogen evolution activity for this catalyst compared to the

pure NiFe-LDH, which it can be because of many parameters such as (a) direct

interfacial contact between NiFe-LDH and carbon with defects on structure, which

increased the electron transfer and decreased the diffusion distance (b) high specific

surface area and high conductive properties of DG, which increased the importance of

this material as building substrates, and (c) layer structure of both LDH and DG, which

increased their performance as hetero-catalysts in water splitting.

53
 Journal Pre-proof

Shen et al. [172] designed a di-functional catalyst based on Zn-Ti-LDH and PdAu

and examined it to produce hydrogen from phenylacetylene. The full conversion of

phenylacetylene with the selectivity of 90% was observed after 6 h. The great selectivity

was recognized to the heterolytic dissociation of H2 at the interface between PdAu alloy

and basic sites of Zn-Ti LDHs and the production of polar hydrogen species.

Additionally, this catalyst was very stable after recycling several times and its reactivity

was slightly decreased (Fig. 27).

of
ro
-p
re
lP
na

Fig. 27. Recyclability of the Zn-Ti-LDH supported by PdAu catalyst. Fig. adapted with
ur

permission from: Ref. [172].

Jo

In a research work, LDH intercalated with sixteen kinds of various amino acids was

studied as a reusable catalyst for S-methylation of thiophenol and also the

chemoselective reaction of O-methylation of phenol under green chemistry [173]. The

amino acid intercalated LDHs revealed a high degree of catalytic action with a good

selectivity in the reaction of O-methylation for phenol using dimethyl carbonate as a

non-toxic reagent. This research considered the green reaction conditions; dimethyl

carbonate as an inexpensive and non-poisonous reagent, no requirement of further

54
 Journal Pre-proof

solvents, simple synthesis of LDH, and reusability of the prepared catalyst.

Accordingly, this research opens a new field to use low-priced LDH for the production

of bio-safe materials in industrial scales.

Mori et al. [174] reported high catalytic efficiency for CO2 hydrogenation through

anchored Ru on the surface of MgAl-LDH under mild situations. Thus, this finding can

develop our understanding of the CO2 as a hydrogen storage system in order to practical

applications.

Morimoto et al. [175] fabricated Mg-Fe(III)-LDH, and then examined its Fe(III)

of
reduction through sugar alcohol at different temperature ranges. It was observed that the

ro
reduction of Fe(III) was done without any changes in the crystal structure of LDH.
-p
Hence, it can be concluded that this material has the potential to be used for the
re
reduction of Fe species in the modern industry.

In a research studied by Dinari and Dadkhah [176], Fe3O4 and Ag NPs (average
lP

particle size = 5.3 nm) were homogeneously incorporated on the surface of LDH (Fig.
na

28). Afterword, a low percentage of this hybrid was dispersed in the starch matrix to

fabricate a low-priced and well-organized catalyst to yield harmless aminophenols from

ur

the deadly nitrophenols with high efficiency.

Jo

Fig. 28. TEM images and particle size distribution of Fe3O4 and Ag NPs incorporated

on LDH. Fig. adapted with permission from: Ref. [176].

55
 Journal Pre-proof

Another research group used dodecylbenzenesulfonate intercalated LDH-carbon dot

NC as an effective heterogeneous catalyst in order to the production of OH radicals

from acidified H2O2 [177]. This research planned a low-cost and green nano-catalyst,

which produced OH radicals through degradation of the dodecylbenzenesulfonate

without any external energy source.

Also, Soliu et al. [178] reported the CoFe-LDH incorporated with carbon felt

(CF) as an appropriate and high-performance cathodic catalyst compared to the

of
homogenous Fe(II) ion catalytic sources for electro-Fenton technology. The highest

ro
efficiency of this catalyst was attained at 90 oC and 7 h with the molar ratio of Co/Fe =
-p
2. Therefore, it can be studied as a well-capable cathodic catalyst to eliminate organic
re
contaminants in the wastewater.

Also, the electrocatalyst behavior of Au NPs dispersed on the surface of NiAl-

lP

LDH was studied for the oxidation of ethanol [179]. The observed results showed the
na

high catalytic performance of this catalyst compared to the pure Au NPs and pure LDH.
ur

5.7. Photocatalytic application

Jo

All over the last decade, many studies have focused on the application of LDH as a

catalyst supporter for improving the photocatalyst activity of nano-metric samples. With

the incorporation of metals on the surface of LDHs, their dispersity and also their

interactions in the reaction are increased, which enhances their surface area to improve

the photocatalytic property. Since the application of LDHs in the photocatalytic area is

remarkable, therefore this section focuses on the main researches that were published in

this area in the last decade.

56
 Journal Pre-proof

LDH with high anion exchange rate hybridized with two complexes of Fe including

[Fe(Cit)2]3- and [Fe(Ox)3]3- to photo-decompose methylene blue in water test solution

[180]. The efficiency of both catalysts for the degradation of methylene blue was

changed at different pHs, and both catalysts showed supreme results. The simple

separation of this heterogeneous LDH-Fe catalyst is another benefit compared to the

other homogenous Fe catalysts.

Mallakpour’s research group [181] examined the VB9 intercalated LDH-TiO2 and

VB9 intercalated LDH-TiO2/crosslinked PVA NC as significant photocatalyst samples

of
in order to photo-degradation of methylene blue. They observed the effect of LDH on

ro
the photo-degradation performance of pure TiO2. The obtained value of the rate
-p
constant (Kapp) for degradation of methylene blue was higher for LDH-VB9 hybridized
re
with TiO2 than others. This finding confirmed the significant role of hybridized LDH-

VB9, which increased the catalyst activity to degrade the methylene blue.
lP

Gong et al. [182] applied Fe-Co-LDH for activation of peroxymonosulfate (PMS),

na

and then used it as a heterogeneous catalyst in order to degradation of Rhodamine B

(RhB). The generated radicals including both SO4.- and OH. promoted the catalytic
ur

activity of this sample for the degradation of RhB pollutants. The possible mechanism
Jo

of Fe-Co-LDH for activation of PMS is shown in Fig. 29. Based on the unique structure

of LDH and due to the standard reduction potentials of metals, the reduction and

oxidation reaction between Fe(II) ion and Co(II) ion can occur, which is responsible for

activation of PMS to produce active radicals including SO4.- and OH. These radicals

degrade the RhB pollutants in the water solution.

57
 Journal Pre-proof

of
ro
Fig. 29. The scheme of PMS activation by heterogeneous catalyst Fe-Co-LDH. Fig.

adapted with permission from: Ref. [182].

-p
re
In a research studied by Darie et al. [183], the effect of tandem Pt and Pt-Ag NPs
lP

doped-LDH as reusable catalysts on the degradation of p-nitrophenol was studied under

solar light. The synergistic activity of Pt-Ag promoted the capacity of LDHs to degrade
na

the p-nitrophenol (77%) compared to Pt alone under solar light. Also, the presence of Fe
ur

in LDH structure significantly reduced the catalytic activity of PT-Ag doped-LDH

Jo

(10%) under solar light, while its catalytic activity was dramatically increased under the

UV-light. It was owing to the changed degradation pathway for p-nitrophenol with Fe.

Guo et al. [184] described the photocatalytic potential of core-shell hierarchical

ZnO@Cu-Zn-Al-LDHs hetero-structures for CO2 reduction. As Fig. 30 shows, because

of the construction of the hierarchical building of ZnO@Cu-Zn-LDH, its yield for

photo-reduction of CO2 to hydrocarbons including CH4 is increased compared to other

materials. This research considered a very notable approach, which is low-cost, and

materials can be recycled and separated in the experimental scale. Also, ZnO with the

58
 Journal Pre-proof

surface defect and electronic construction could promote the photocatalytic properties of

LDHs.

of
ro
-p
Fig. 30. CH4 evolution of the photocatalytic conversion of CO2 over ZnO, LDHs, and

ZnO@LDHs catalysts under visible light. R = rod-liked and B = belt-liked structure.

re

Fig. adapted with permission from: Ref. [184].

lP

Also, Ti-doped-MgFe LDH was effectively examined in order to adsorption and

na

photo-degradation of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) [185]. In the usual

ur

condition, this catalyst adsorbed the 2,4,5-T molecules less than 50%, but the amount of
Jo

photo-Fenton-like degradation of 2,4,5-T was increased from 81 to 94%.

Likewise, Ti-doped LDH material was investigated in order to degradation of Azo

dyes by Xia et al. [186]. This material showed the high photocatalytic efficiency for two

organic dyes: CeO2/ZnTi-LDH sample revealed the maximum photocatalytic activity

for methyl orange and methylene blue among all samples. Also, Zn/Al-Ti/Schiff-base-

LDHs with high efficiency were recycled at least three times.

Another research considered highly efficient NiCo-LDH/P-CdS hybrid through in-

situ loading LDH on the surface of CdS using the p-doping approach [187]. The

presence of the loaded LDH not only decreased light corrosion of the CdS but also

59
 Journal Pre-proof

increased its separation efficiency. Also, with the loaded LDH, the H2 production of

CdS was increased about 45 times compared to the pure CdS.

Huang’s research group [188] deliberated the dimethyl phthalate (DMP) gegradation

under LDH/TiO2 and SDS-LDH/TiO2 photocatalysts. In both cases, LDH increased the

TiO2 activity to degrade the DMP molecule, owing to the more produced hydroxyl

radicals of the LDH surface. The proposed mechanism of the photo-degradation of

DMP with SDS-LDH/TiO2 material is shown in equations 7-16:

SDS-LDHs/TiO2 + hʋ → SDS-LDHs/TiO2 (e- + h+) (7)

of
h+ + H2O → .OH + H+ (8)

ro
h+ + OH → .OH -p (9)

h+ + SDS-LDHs≡ M-OH → .OH (10)

re
O2 + e-→ O2.- (11)

O2 + 2H+ +2e-→ H2O2 (12)

lP

h+ + DMP→ oxidation products (13)

na

e- + DMP→ reduction products (14)

.
OH + DMP→ CO2 + H2O (15)
ur

O2.- + DMP→ CO2 + H2O (16)

Jo

according to this mechanism, the produced radicals (.OH and O2.-) and holes (h+) in the

presence of oxidative source are responsible for the degradation of DMP.

Also, Mohamed et al. [189] examined the photo-degradation of safranin dye through

polypyrrole nanofiber/Zn-Fe LDH sample. The high surface area and low band gap of

this catalyst increased the safranin degradation with the reusability of six steps. As

observed in Fig. 31, in the presence of visible light, the produced radicals decompose

the poisonous safranin dye to other materials with lower toxicity.

60
 Journal Pre-proof

of
ro
Fig. 31. The schematic photo-degradation of safranin dye using polypyrrole

nanofiber/Zn-Fe LDH NC. Fig. adapted with permission from: Ref. [189].
-p
re
Gilea et al. [190] modified LDH through in-situ growth of Ag NPs on its
lP

surface, and they studied the effect of the Ag NPs concentration and calcinated

temperature of Ag NPs/LDH on the photo-degradation of phenol under solar light. As

na

Fig. 32 shows, TEM and high-resolution TEM (HRTEM) photographs demonstrated a

ur

clear lattice fringe with a d-spacing of 0.27 nm, corresponding to the presence of Ag2O

in the structure and also the formation of heterojunction [190]. They showed that the
Jo

highest degradation of phenol was obtained for Ag NP/ZnAl-LDH with 2.9 wt% of Ag

NPs and the calcinated temperature of 750 oC.

61
 Journal Pre-proof

of
ro
-p
re
Fig. 32. TEM image and (inset) higher magnification of HRTEM image of Ag

NP/MgAl-LDH. Fig. adapted with permission from: Ref. [190].

lP
na

5.8. Bioactive application

From the past, human has suffered from bone pains such as bone fractures. Fracture
ur

of a small bone can be repaired easily, but when a large bone is fractured it is very
Jo

difficult to be repaired again. Hydroxyapatite (HA), one important part of the bone, has

chemical structure similar to natural bone and teeth and it is represented with common

formula of Ca10(OH)2(PO4)6. Thus, this compound has great potentials in medical

applications such as tissue engineering and surface engineering [191-193]. Recently,

laboratory synthesis of HAs is considered as a novel research in many studies. In the

last decade, because of the not-toxic and biocompatibility of modified LDHs, they have

been successfully studied to be examined as low-priced scaffolds for the formation of

the HAs to be replaced with natural bones. Rezvani and Akbari [194] considered the

62
 Journal Pre-proof

HA-modified-LDH as a cost-effective, green, non-poisonous, and innovative attitude to

fabricate HA compounds. The FE-SEM results showed the precipitation of HAs on the

surface of HA-modified-LDH after immersing in the simulated body, which this finding

confirmed the bioactive potential of this material to be used in medical fields.

Fayyazbakhsh et al. investigated the effect of HA modified-LDH [LDH (75%) and

HA (25%)] on the bioactivity of gelatine [195]. As shown in FE-SEM images of

samples (Fig. 33), both LDH-HA/gelatine and LDH/gelatine NCs show the porous

structure similar to the natural bone, though the porosity of LDH-HA/gelatine is

of
decreased. The results of the bioactivity test exhibited that after immersing samples in

ro
simulated body fluid, the needle-like secondary HAs were grown on the surface of both
-p
NCs. Also, they observed that with the increasing time from 1 to 14 to 21 days, the
re
degradation of pores was happened, and also with this degradation, the ratio of needle-

like prepared-HA crystals increased. After 21 days, the length and diameter were higher
lP

for LDH-HA/gelatine, which confirms its higher bioactivity.

na
ur
Jo

Fig. 33. Micrographs of specimens: (a) pure LDH/GEL scaffold, (b) LDH-HA/GEL

scaffold, (c) natural bone microstructure for comparison with synthetic scaffolds. Fig.

adapted with permission from: Ref. [195].

5.9. Solar cell application

63
 Journal Pre-proof

Nowadays, it is a great challenge for the scientist to produce catalytic samples that

can control the environmental issues related to the combustion of fossil fuels. Also, it is

very important to examine methods and materials that are low-priced and economic to

produce clean fuels (like hydrogen and oxygen) with high efficiency. Up to now,

different materials (like NPs such as α-Fe2O3, WO3, and BiVO4) were examined to

photoelectrochemical (PEC) water splitting, but it is observed that the efficiency of

these materials is not remarkable [196, 197]. Furthermore, the expensive cost of

catalytic materials based on Ir limited their application to be used in PEC water splitting

of
[198]. Thus, many studies focused on the modified LDHs as low-priced catalysts with

ro
high efficiency in the oxidation of water. -p
Foruzin et al. [199] prepared TiO2@ZnAl-LDH, calcined it at high temperature for
re
achieving the TiO2@MMO NCs, and then it was used as a photo-anode with a great

degree of conversion efficiency. The obtained results indicated the development of the
lP

dye-sensitized solar cell.

na

In a research, Luo et al. [200] examined the LDH intercalated with phosphate,

phosphite, and hypophosphite as low-cost and available electro-catalysts for oxygen

ur

evolution. According to the observed results, the existence of anionic phosphorus

Jo

molecules improved the oxygen evolution reaction activity due to the electronic

construction of LDH layers. Therefore, these materials have the potential to apply and

organize progressive electro-catalysts towards worldwide clean-energy production.

Mustafa et al. [201] indicated that the Ni-Fe-LDH was able to successfully improve

the PEC water splitting application of ZnO NPs. They observed that the current

conversion efficiency of Ni-Al-LDH/ZnO was 82% compared to the 70% of pure ZnO

NPs in similar conditions. Thus, this research suggests a low-priced and earth-abundant

64
 Journal Pre-proof

route for the synthesis of photo-anode material with high efficiency to be applied in

solar cells.

Bai et al. [198] studied the effect of Fe2O3/BiVO4/LDH heterojunction as a powerful

photoanode and observed that the produced sample has numerous effects for PEC water

splitting performance. They observed that the photocurrent density and PCE water

splitting property of Fe2O3/BiVO4/LDH heterojunction were increased in comparison

with the α-Fe2O3 about 4.25 and 3.70 times, respectively.

Zhou et al. [70] observed that the S2- modified NiV-LDH was very porous and its

of
specific capacitance was increased (2270.4 F g−1) compared to the pristine NiV-LDH

ro
(1502 F g−1). -p
Also, Zhou et al. [202] synthesized LDH samples on the surface of the Co3O4 on
re
Ni foam and the produced composite was examined as a battery-type electrode sample

for supercapacitors. The Co3O4@CoNi-LDH showed a specific capacitance of 2676.9 F

lP

g−1 with great cycling stability compared to the pure Co3O4.

na

A reported study by Si et al. [203] showed that the Ni-Al-LDH coupled with

graphdiyne and grown on the surface of copper foam had great potentials to be used in
ur

both hydrogen (163 mV) and oxygen (220 mV) evaluations, which increased its PEC
Jo

water splitting performance.

Furthermore, another work showed when the Ni-Al-LDH was loaded on the

surface of BiVO4, it was able to promote the light-absorption capacities and also

increased the photocurrent response of the BiVO4 [204]. Also, the obtained PEC

hydrogen evolution was higher for the Ni-AL-LDH/BiVO4 in comparison with the pure

BiVO4, Ni(OH)2/BiVO4, and Fe(OH)2/BiVO4.

Yu’s research group [205] indicated the great PEC water splitting application of

the α-Fe2O3/ultrathin NiMn LDH compared to the pristine α-Fe2O3 (about 15-fold), and

65
 Journal Pre-proof

also Chong et al. [206] showed that the PEC water splitting application of the An−-

CoAl-LDHs/α-Fe2O3 was different by An- (An- = NO3−, CO32−, SO42− and PO43−). They

showed when the PO43− was examined in the LDH structure, the highest value of

photocurrent density was obtained (4.30 mA cm−2), which it was 5.6 times higher than

the pristine α-Fe2O3.

6. Conclusions and future challenges

LDHs are used as a new developing type of the most advantageous nanostructured

of
materials for constructing functionalized layered crystal samples. These materials are

ro
low-priced, biocompatible, and no toxic, and furthermore, due to their unique
-p
properties, they are incredibly interested in the new studies of researchers. Currently,
re
modification and intercalation of LDH with appropriate organic and inorganic materials

have improved their physio-chemical features, enlarged their gallery space, and also in
lP

some cases promoted their organo-phillicity to increase their applications in modern

na

technologies including water purification, energy storage, biomedical areas, material

engineering, and so on. These results are because of the high surface area, tunable
ur

property, high anion exchange behavior, and structural diversity of LDHs, which
Jo

promoted strong interactions of the inorganic host with the guest compounds. While

modification of LDHs may not be appropriate always, but it is a great idea to be

considered deeply with standardization parameters in the future studies. Accordingly,

with these findings, the author suggests using the modified LDH in the industrial large

scales, which is economic and time-saving, high efficient, eco-friendly, and produce

clean energy. Additionally, since the LDH synthesis process does not need a highly

complex and harsh condition, hence, future strategies can be employed to prepare

multifunctional LDHs with controlled properties and applications.

66
 Journal Pre-proof

Declaration of Interest

There is no declaration interest

Acknowledgments

Authors thank the financial support from Research Affairs Division Isfahan

University of Technology, Isfahan, Iran; Iran Nanotechnology Initiative Council,

Tehran, Iran; and National Elite Foundation , Tehran, Iran. Furthermore, authors would

like to thank Dr. F. Tabesh, Dr. V. Behranvand, Miss F. Sirous, and Miss E. Azadi for

of
their great help.

ro
-p
Appendix A. Nomenclature
re
AFM Atomic force microscopy

CMC Carboxymethyl cellulose

lP

DSC Differential scanning calorimetry

na

DMP Dimethyl phthalate

DPA Diphenylamine-4-sulfonate
ur

VLDH Disodium vanillin L-aspartic acid

Jo

DS Dodecyl sulfonate

EDTA Ethylene diamine tetraacetic acid

FE-SEM Field emission scanning electron microscopy

FA Fumarate

HA Hydroxyapatite

IL Ionic liquid

LDH Layered double hydroxide

LDO Layered double oxide

67
 Journal Pre-proof

MOF Metal-organic framework

MTX Methotrexatum

MTMS Methyltrimethoxysilane

MWNT Multiwalled carbon nanotube

NC Nanocomposite

NP Nanoparticle

NGO N-doped graphene oxide

PEC Photoelectrochemical

of
PAI Poly(amide-imide)

ro
PEG Poly(ethylene glycol) -p
PS Polystyrene
re
PLA Poly(L-lactide)

PCL Poly(ε-caprolactone)
lP

RhB Rhodmine B
na

SDBS Sodium dodecyl benzene sulfonate

SDS Sodium dodecyl sulfate

ur

TA Terephthalate
Jo

TGA Thermogravimetric analysis

TEM Transmission electron microscopy

TEVS Triethoxyvinylsilane

VC Vitamin C

VB9 Vitamin B9

XRD X-ray powder diffraction

KH560 γ-(2,3-epoxypropoxy) propyltrimethoxysilane

EHP 2-ethylhexyl hydrogenphosphate

68
 Journal Pre-proof

DDA 4,4-diaminostilbene-2,2-disulfonic acid

of
Professor Shadpour Mallakpour, organic polymer chemist, graduated from chemistry
department, University of Florida (UF), Gainesville, Florida, USA in 1984. He spent

ro
two years as a post-doc at UF. He has joined the department of chemistry, Isfahan
-p
University of Technology (IUT), Iran, since 1986. He held several positions such as the
chairman of the department of chemistry and deputy of research, department of
re
chemistry at IUT. From 1994-1995 he worked as a visiting professor, University of
Mainz, Germany, and from 2003-2004 as a visiting professor, Virginia Tech,
lP

Blacksburg, USA. He has published more than 820 journal papers and more than 400
conference papers and has got more than 30 items of awards. The most important award
na

to him was given for the selection of the first laureate on fundamental research, at 21 st
Khwarizmi International award in 2008. He is listed as the Top 1% Scientists in
ur

Chemistry in ISI Essential Science Indicators Since 2003. He was selected as academic
guest of the 59th Meeting of Nobel Prize Winners in Chemistry, 2009, at Lindau,
Jo

Germany. He presented many lectures as an invited or keynote speaker in different

national and international conferences or universities. He was a member of organizing
and scientific committees for many national and international conferences. He was also
the chairperson of many national and international meetings. In recent years, he has
focused on preparation and characterization of polymer-based nanocomposites to be
used as bioactive materials as well as adsorbents and photocatalyst for remediation
technology.

69
 Journal Pre-proof

Masoud Hatami is PhD student of organic-polymer chemistry at Isfahan University of

Technology (IUT). In 2012, he received a BSc degree in chemistry from Yasouj
University, Iran, and also in 2014, he received a MSc degree in organic-polymer
chemistry from IUT. Her study interests include intercalation and surface modification
of LDH nono-clays, surface functionalization of metal oxide nanoparticles, and also
preparation, characterization and applications of the novel polymeric

of
bionanocomposites.

ro
-p
re
lP
na
ur

Chaudhery Mustansar Hussain, PhD is an Adjunct Professor, Academic Advisor and

Jo

Director of Chemistry & EVSc Labs in the Department of Chemistry & Environmental
Sciences at the New Jersey Institute of Technology (NJIT), Newark, New Jersey, USA.
His research is focused on the applications of Nanotechnology & Advanced Materials,
Environmental Management, Analytical Chemistry and Various Industries. Dr. Hussain
is the author of numerous papers in peer-reviewed journals as well as prolific author and
editor of several scientific monographs and handbooks in his research areas published
with ELSEVIER, Royal Society of Chemistry, John Wiley & sons, CRC, Springer etc

References

[1] Shahadat M, Khan MZ, Rupani PF, Embrandiri A, Sultana S, Ahammad SZ, et al. A
critical review on the prospect of polyaniline-grafted biodegradable
nanocomposite. Adv Colloid Interface Sci 2017;249:2-16.

70
 Journal Pre-proof

[2] Lu Y, Dong W, Ding J, Wang W, Wang A. 10 -Hydroxyapatite nanomaterials:

Synthesis, properties, and functional applications. In: Wang A, Wang W,
(editors). Nanomaterials from clay minerals. Amsterdam, Netherland, Elsevier,
2019. p. 485-536.
[3] Gregorczyk K, Knez M. Hybrid nanomaterials through molecular and atomic layer
deposition: Top down, bottom up, and in-between approaches to new materials.
Prog Mater Sci 2016;75:1-37.
[4] Mallakpour S, Naghdi M. Polymer/SiO2 nanocomposites: Production and
applications. Prog Mater Sci 2018;97:409-47.
[5] Zand Z, Salimi P, Mohammadi MR, Bagheri R, Chernev P, Song Z, et al. Nickel-
Vanadium layered double hydroxide under water-oxidation reaction: New
findings and challenges. ACS Sustain Chem Eng 2019;7:17252-62.
[6] Prasad C, Tang H, Liu QQ, Zulfiqar S, Shah S, Bahadur I. An overview of
semiconductors/layered double hydroxides composites: Properties, synthesis,
photocatalytic and photoelectrochemical applications. J Mol Liq

of
2019;289:111114.
[7] Wang D, Peng F, Li J, Qiao Y, Li Q, Liu X. Butyrate-inserted Ni-Ti layered double

ro
hydroxide film for H2O2-mediated tumor and bacteria killing. Mater Today
2017;20:238-57.
[8] Mohapatra L, Parida K. A review on the recent progress, challenges and perspective
-p
of layered double hydroxides as promising photocatalysts. J Mater Chem A
2016;4:10744-66.
re
[9] Jeon CW, Lee SS, Park IK. Flexible visible-blind ultraviolet photodetectors based
on ZnAl-layered double hydroxide nanosheet scroll. ACS Appl Mater Interfaces
2019;11:35138-45.
lP

[10] Long X, Wang Z, Xiao S, An Y, Yang S. Transition metal based layered double
hydroxides tailored for energy conversion and storage. Mater Today 2016;19:213-
26.
na

[11] Song B, Zeng Z, Zeng G, Gong J, Xiao R, Ye S, et al. Powerful combination of g-

C3N4 and LDHs for enhanced photocatalytic performance: A review of strategy,
synthesis, and applications. Adv Colloid Interface Sci 2019;272:101999.
ur

[12] Matusinovic Z, Lu H, Wilkie CA. The role of dispersion of LDH in fire retardancy:
The effect of dispersion on fire retardant properties of polystyrene/Ca-Al layered
double hydroxide nanocomposites. Polym Degrad Stab 2012;97:1563-8.
Jo

[13] Bezerra DM, Rodrigues JE, Assaf EM. Structural, vibrational and morphological
properties of layered double hydroxides containing Ni2+, Zn2+, Al3+ and Zr4+
cations. Mater Charact 2017;125:29-36.
[14] Du P, Liu C, Qiu S, Liu G, Zhao H. Surface modification of Mg/Al layered double
hydroxide by camphorsulfonic acid doped polyaniline and its applications for
anticorrosive coating. Surf Topograph 2018;6:1-12.
[15] Liu F, Chen Y, Liu Y, Bao J, Han M, Dai Z. Integrating ultrathin and modified
NiCoAl-layered double-hydroxide nanosheets with N-doped reduced graphene
oxide for high-performance all-solid-state supercapacitors. Nanoscale
2019;11:9896-905.
[16] Kim TH, Oh JM. Dual nutraceutical nanohybrids of folic acid and calcium
containing layered double hydroxides. J Solid State Chem 2016;233:125-32.
[17] Zhao M, Zhao Q, Li B, Xue H, Pang H, Chen C. Recent progress in layered double
hydroxide based materials for electrochemical capacitors: Design, synthesis and
performance. Nanoscale 2017;9:15206-25.

71
 Journal Pre-proof

[18] Mishra G, Dash B, Pandey S. Layered double hydroxides: A brief review from
fundamentals to application as evolving biomaterials. Appl Clay Sci
2018;153:172-86.
[19] Rives V, del Arco M, Martín C. Layered double hydroxides as drug carriers and for
controlled release of non-steroidal antiinflammatory drugs (NSAIDs): A review. J
Control Rel 2013;169:28-39.
[20] Gu Z, Atherton JJ, Xu ZP. Hierarchical layered double hydroxide nanocomposites:
structure, synthesis and applications. Chem Commun 2015;51:3024-36.
[21] Kuthati Y, Kankala RK, Lee C-H. Layered double hydroxide nanoparticles for
biomedical applications: Current status and recent prospects. Appl Clay Sci
2015;112:100-16.
[22] Peng C, Xing H, Xue Y, Wang J, Li J, Wang E. Ratiometric sensing of alkaline
phosphatase based on the catalytical activity from Mn-Fe layered double
hydroxide nanosheets. Nanoscale 2020;12:2022-7.
[23] Benício LPF, Silva RA, Lopes JA, Eulálio D, Santos RMMd, Aquino LAd, et al.

of
Layered double hydroxides: nanomaterials for applications in agriculture. Revista
Brasileira de Ciência do Solo. 2015;39:1-13.

ro
[24] Yao W, Yu S, Wang J, Zou Y, Lu S, Ai Y, et al. Enhanced removal of methyl
orange on calcined glycerol-modified nanocrystallined Mg/Al layered double
hydroxides. Chem Eng J 2017;307:476-86.
-p
[25] Liang R, Xu S, Yan D, Shi W, Tian R, Yan H, et al. CdTe quantum dots/layered
double hydroxide ultrathin films with multicolor light emission via layer‐by‐layer
re
assembly. Adv Function Mater 2012;22:4940-8.
[26] Purohit PJ, Wang DY, Wurm A, Schick C, Schönhals A. Comparison of thermal
and dielectric spectroscopy for nanocomposites based on polypropylene and
lP

layered double hydroxide-proof of interfaces. Eur Polym J 2014;55:48-56.

[27] Yu IKM, Hanif A, Tsang DCW, Shang J, Su Z, Song H, et al. Tuneable
functionalities in layered double hydroxide catalysts for thermochemical
na

conversion of biomass-derived glucose to fructose. Chem Eng J 2019:122914.

[28] Darmograi G, Prelot B, Geneste A, Martin-Gassin G, Salles F, Zajac J. How does
competition between anionic pollutants affect adsorption onto Mg-Al layered
ur

double hydroxide? Three competition schemes. The J Phys Chem C

2016;120:10410-8.
[29] Galvão TL, Neves CS, Caetano AP, Maia F, Mata D, Malheiro E, et al. Control of
Jo

crystallite and particle size in the synthesis of layered double hydroxides:

Macromolecular insights and a complementary modeling tool. J Colloid Interface
Sci 2016;468:86-94.
[30] Zhang R, Shao M, Xu S, Ning F, Zhou L, Wei M. Photo-assisted synthesis of zinc-
iron layered double hydroxides/TiO2 nanoarrays toward highly-efficient
photoelectrochemical water splitting. Nano Energy 2017;33:21-8.
[31] Dong S, Guan W, Lu C. Quantum dots in organo-modified layered double
hydroxide framework-improved peroxynitrous acid chemiluminescence for nitrite
sensing. Sens Actuators B 2013;188:597-602.
[32] Carja G, Delahay G. Mesoporous mixed oxides derived from pillared oxovanadates
layered double hydroxides as new catalysts for the selective catalytic reduction of
NO by NH3. Appl Cat B 2004;47:59-66.
[33] Everaert M, Warrinnier R, Baken S, Gustafsson JP, De Vos D, Smolders E.
Phosphate-exchanged Mg-Al layered double hydroxides: a new slow release
phosphate fertilizer. ACS Sustain Chem Eng 2016;4:4280-7.

72
 Journal Pre-proof

[34] Bukhtiyarova MV. A review on effect of synthesis conditions on the formation of

layered double hydroxides. J Solid State Chem 2019;269:494-506.
[35] Inayat A, Klumpp M, Schwieger W. The urea method for the direct synthesis of
ZnAl layered double hydroxides with nitrate as the interlayer anion. Appl Clay Sci
2011;51:452-9.
[36] Rives V, Arco M, Martín. Intercalation of drugs in layered double hydroxides and
their controlled release: A review. Appl Clay Sci 2014;88-89: 239-269.
[37] Deng X, Huang J, Wan H, Chen F, Lin Y, Xu X, et al. Recent progress in
functionalized layered double hydroxides and their application in efficient
electrocatalytic water oxidation. J Energy Chem 2019;32:93-104.
[38] Qu J, Zhang Q, Li X, He X, Song S. Mechanochemical approaches to synthesize
layered double hydroxides: a review. Appl Clay Sci 2016;119:185-92.
[39] Chatterjee A, Bharadiya P, Hansora D. Layered double hydroxide based
bionanocomposites. Appl Clay Sci 2019;177:19-36.
[40] Theiss FL, Ayoko GA, Frost RL. Removal of boron species by layered double

of
hydroxides: a review. J Colloid Interface Sci 2013;402:114-21.
[41] Mallakpour S, Rashidimoghadam S. Recent developments in the synthesis of

ro
hybrid polymer/clay nanocomposites: Properties and applications. In: Thakur VK,
Thakur MK, Pappu A, (editors). Hybrid polymer composite materials:
Applications. Woodhead Publishing, Sawston, Cambridge, Elsevier, 2017.
-p
Chapter 8. p. 227–65.
[42] Chubar N, Gilmour R, Gerda V, Mičušík M, Omastova M, Heister K, et al.
re
Layered double hydroxides as the next generation inorganic anion exchangers:
Synthetic methods versus applicability. Adv Colloid Interface Sci 2017;245:62-
80.
lP

[43] Mallakpour S, Hatami M. Condensation polymer/layered double hydroxide NCs:

Preparation, characterization, and utilizations. Eur Polym J 2017;90:273-300.
[44] Kameda T, Shimmyo T, Yoshioka T. Preparation of Zn-Al layered double
na

hydroxide intercalated with triethylenetetramine-hexaacetic acid by

coprecipitation: uptake of rare-earth metal ions from aqueous solutions. RSC Adv
2014;4:45995-6001.
ur

[45] Theiss FL, Ayoko GA, Frost RL. Synthesis of layered double hydroxides
containing Mg2+, Zn2+, Ca2+ and Al3+ layer cations by co-precipitation methods-A
review. Appl Surf Sci 2016;383:200-13.
Jo

[46] Nhlapo NS. Intercalation of fatty acids in a layered double hydroxide. In the
Department of Chemistry, University of Pretoria, Faculty of Natural and
Agricultural Sciences, 2009, pp. 1-126.
[47] Lyu B, Wang YF, Gao DG, Ma JZ, Li Y. Intercalation of modified zanthoxylum
bungeanum maxin seed oil/ stearate in layered double hydroxide: Toward flame
retardant nanocomposites. J Environ Manag 2019;238:235-42.
[48] Gao X, Chen L, Xie J, Yin Y, Chang T, Duan Y, et al. In vitro controlled release of
vitamin C from Ca/Al layered double hydroxide drug delivery system. Mater Sci
Eng C 2014;39:56-60.
[49] Wang X, Kalali EN, Wang DY. Renewable cardanol-based surfactant modified
layered double hydroxide as a flame retardant for epoxy resin. ACS Sustain Chem
Eng 2015;3:3281-90.
[50] Zhang C, Yu J, Feng K, Xue L, Xie D. Synthesis and characterization of
triethoxyvinylsilane surface modified layered double hydroxides and application
in improving UV aging resistance of bitumen. Appl Clay Sci 2016;120:1-8.

73
 Journal Pre-proof

[51] Kameda T, Takaizumi M, Kumagai S, Saito Y, Yoshioka T. Uptake of Ni 2+ and

Cu2+ by Zn-Al layered double hydroxide intercalated with carboxymethyl-
modified cyclodextrin: Equilibrium and kinetic studies. Mater Chem Phys
2019;233:288-95.
[52] Gao H, Cao Y, Chen Y, Liu Z, Guo M, Ding S, et al. Ultrathin NiFe-layered double
hydroxide decorated NiCo2O4 arrays with enhanced performance for
supercapacitors. Appl Surf Sci 2019;465:929-36.
[53] Sanati S, Rezvani Z. Ultrasound-assisted synthesis of NiFe-layered double
hydroxides as efficient electrode materials in supercapacitors. Ultrason Sonochem
2018;48:199-206.
[54] Sanati S, Rezvani Z. Ultrasound-assisted synthesis of NiFe-layered double
hydroxides as efficient electrode materials in supercapacitors. Ultrason Sonochem
2018;48:199-206.
[55] Mallakpour S, Dinari M, Hatami M. Novel nanocomposites of poly(vinyl alcohol)
and Mg-Al layered double hydroxide intercalated with diacid N-

of
tetrabromophthaloyl-aspartic. J Therm Anal Calorim 2015;120:1293-302.
[56] Baruah A, Mondal S, Sahoo L, Gautam UK. Ni-Fe-layered double hydroxide/N-

ro
doped graphene oxide nanocomposite for the highly efficient removal of Pb(II)
and Cd(II) ions from water. J Solid State Chem 2019;280:120963.
[57] Liu SQ, Li SP, Li XD. Intercalation of methotrexatum into layered double
-p
hydroxides via exfoliation-reassembly process. Appl Surf Sci 2015;330:253-61.
[58] Ye T, Huang W, Zeng L, Li M, Shi J. CeO2-x platelet from monometallic cerium
re
layered double hydroxides and its photocatalytic reduction of CO2. Appl Cat B
2017;210:141-8.
[59] Darmograi G, Prelot B, Layrac G, Tichit D, Martin-Gassin G, Salles F, et al. Study
lP

of adsorption and intercalation of orange-type dyes into Mg-Al layered double

hydroxide. The J Phys Chem C 2015;119:23388-97.
[60] Asif M, Aziz A, Azeem M, Wang Z, Ashraf G, Xiao F, et al. A review on
na

electrochemical biosensing platform based on layered double hydroxides for small

molecule biomarkers determination. Adv Colloid Interface Sci 2018;262:21-38.
[61] He J, Wei M, Li B, Kang Y, Evans DG, Duan X. Preparation of layered double
ur

hydroxides. Layered double hydroxides: Springer, Berlin, Heidelberg, 2006. p.

89-119.
[62] Evans DG, Duan X. Preparation of layered double hydroxides and their
Jo

applications as additives in polymers, as precursors to magnetic materials and in

biology and medicine. Chem Commun 2006:485-96.
[63] Mallakpour S, Dinari M. Facile synthesis of nanocomposite materials by
intercalating an optically active poly(amide-imide) enclosing (L)-isoleucine
moieties and azobenzene side groups into a chiral layered double hydroxide.
Polymer 2013;54:2907-16.
[64] San Román MS, Holgado MJ, Salinas B, Rives V. Drug release from layered
double hydroxides and from their polylactic acid (PLA) nanocomposites. Appl
Clay Sci 2013;71:1-7.
[65] Moyo L, Ray SS, Sebati W, Ojijo V. The influence of filler surface modification on
mechanical and material properties of layered double hydroxide‐containing
polypropylene composites. J Appl Polym Sci 2017;134:45024.
[66] Conterosito E, Gianotti V, Palin L, Boccaleri E, Viterbo D, Milanesio M. Facile
preparation methods of hydrotalcite layered materials and their structural
characterization by combined techniques. Inorg Chim Acta 2018;470:36-50.

74
 Journal Pre-proof

[67] Li K, Kumada N, Yonesaki Y, Takei T, Kinomura N, Wang H, et al. The pH

effects on the formation of Ni/Al nitrate form layered double hydroxides (LDHs)
by chemical precipitation and hydrothermal method. Mater Chem Phys
2010;121:223-9.
[68] Wang X, Zhang J, Yang S, Yan H, Hong X, Dong W, et al. Interlayer space
regulating of NiMn layered double hydroxides for supercapacitors by controlling
hydrothermal reaction time. Electrochim Acta 2019;295:1-6.
[69] Li X, Yang Z, Qi W, Li Y, Wu Y, Zhou S, et al. Binder-free Co3O4@NiCoAl-
layered double hydroxide core-shell hybrid architectural nanowire arrays with
enhanced electrochemical performance. Appl Surf Sci 2016;363:381-8.
[70] Zhou P, Wang C, Liu Y, Wang Z, Wang P, Qin X, et al. Sulfuration of NiV-layered
double hydroxide towards novel supercapacitor electrode with enhanced
performance. Chem Eng J 2018;351:119-26.
[71] Gholami P, Dinpazhoh L, Khataee A, Hassani A, Bhatnagar A. Facile
hydrothermal synthesis of novel Fe-Cu layered double hydroxide/biochar

of
nanocomposite with enhanced sonocatalytic activity for degradation of cefazolin
sodium. J Hazard Mater 2019:120742.

ro
[72] Li D, Xu X, Xu J, Hou W. Poly(ethylene glycol) haired layered double hydroxides
as biocompatible nanovehicles: Morphology and dispersity study. Colloids Surf A
2011;384:585-91.
-p
[73] Baig N, Sajid M. Applications of layered double hydroxides based electrochemical
sensors for determination of environmental pollutants: A review. Trends Environ
re
Anal Chem 2017;16:1-15.
[74] Othman M, Helwani Z, Fernando W. Synthetic hydrotalcites from different routes
and their application as catalysts and gas adsorbents: a review. Appl Organometal
lP

Chem 2009;23:335-46.
[75] Kameda T, Oba J, Yoshioka T. Removal of boron and fluoride in wastewater using
Mg-Al layered double hydroxide and Mg-Al oxide. J Environ Manag
na

2017;188:58-63.
[76] Costantino U, Marmottini F, Nocchetti M, Vivani R. New synthetic routes to
hydrotalcite‐like compounds-characterisation and properties of the obtained
ur

materials. Eur J Inorg Chem 1998;1998:1439-46.

[77] Milanovic N. Synthesis, structural and magnetic properties of layered double
hydroxides, Master thesis in Materials Science and Nanotechnology, Department
Jo

of Physics, University of OSLO, 2016, pp. 1-33.

[78] Wu S, Hui K, Hui K. One-dimensional core-shell architecture composed of silver
nanowire@hierarchical nickel-aluminum layered double hydroxide nanosheet as
advanced electrode materials for pseudocapacitor. The J Phys Chem C
2015;119:23358-65.
[79] Grover A, Kaur R, Mohiuddin I, Malik AK, Aulakh JS, Tsang YF, et al.
Surfactant-modified Zn/Al-layered double hydroxides for efficient extraction of
alkyl phenols from aqueous samples. Environ Res 2019;177:108605.
[80] Grover A, Mohiuddin I, Malik AK, Aulakh JS, Kim KH. Zn-Al layered double
hydroxides intercalated with surfactant: Synthesis and applications for efficient
removal of organic dyes. J Clean Prod 2019;240:118090.
[81] Liu J, Song J, Xiao H, Zhang L, Qin Y, Liu D, et al. Synthesis and thermal
properties of ZnAl layered double hydroxide by urea hydrolysis. Powder Technol
2014;253:41-5.

75
 Journal Pre-proof

[82] Chilukoti S, Thangavel T. Enhanced adsorption of Congo red on microwave

synthesized layered Zn-Al double hydroxides and its adsorption behaviour using
mixture of dyes from aqueous solution. Inorg Chem Commun 2019;100:107-17.
[83] Allou NgB, Saikia J, Bordoloi P, Yadav A, Pal M, Goswamee RL. Layered double
hydroxide and microwave assisted functionalized carbon based nanocomposites as
controlled release vehicle for antibiotics. J Drug Deliv Sci Technol 2019;49:243-
53.
[84] Fang J, Li M, Li Q, Zhang W, Shou Q, Liu F, et al. Microwave-assisted synthesis
of CoAl-layered double hydroxide/graphene oxide composite and its application
in supercapacitors. Electrochim Acta 2012;85:248-55.
[85] Cosano D, Esquivel D, Romero FJ, Jiménez-Sanchidrián C, Ruiz JR. Microwave-
assisted synthesis of hybrid organo-layered double hydroxides containing cholate
and deoxycholate. Mater Chem Phys 2019;225:28-33.
[86] Lonkar SP, Raquez JM, Dubois P. One-pot microwave-assisted synthesis of
graphene/layered double hydroxide (LDH) nanohybrids. Nano-Micro Lett

of
2015;7:332-40.
[87] Zhang G, Hu L, Zhao R, Su R, Wang Q, Wang P. Microwave-assisted synthesis of

ro
ZnNiAl-layered double hydroxides with calcination treatment for enhanced PNP
photo-degradation under visible-light irradiation. J Photochem Photobiol A
2018;356:633-41.
-p
[88] Qiao C, Zhang Y, Zhu Y, Cao C, Bao X, Xu J. One-step synthesis of Zinc-Cobalt
layered double hydroxide (Zn-Co-LDH) nanosheets for high-efficiency oxygen
re
evolution reaction. J Mater Chem A 2015;3:6878-83.
[89] Siebecker MG, Li W, Sparks DL. The important role of layered double hydroxides
in soil chemical processes and remediation: what we have learned over the past 20
lP

years. Adv Agron 2018;147:1-59.

[90] Smalenskaite A, Salak AN, Ferreira MGS, Skaudzius R, Kareiva A. Sol-gel
synthesis and characterization of hybrid inorganic-organic Tb(III)-terephthalate
na

containing layered double hydroxides. Optic Mater 2018;80:186-96.

[91] Chubar N, Gerda V, Megantari O, Mičušík M, Omastova M, Heister K, et al.
Applications versus properties of Mg-Al layered double hydroxides provided by
ur

their syntheses methods: alkoxide and alkoxide-free sol-gel syntheses and

hydrothermal precipitation. Chem Eng J 2013;234:284-99.
[92] Smalenskaite A, Vieira DEL, Salak AN, Ferreira MGS, Katelnikovas A, Kareiva
Jo

A. A comparative study of co-precipitation and sol-gel synthetic approaches to

fabricate cerium-substituted MgAl layered double hydroxides with luminescence
properties. Appl Clay Sci 2017;143:175-83.
[93] Donaldson L. Nanocomposite material that protects against laser attack. Mater
Today 2019;31:5.
[94] Mallakpour S, Dinari M, Hatami M. Modification of Mg/Al-layered double
hydroxide with L-aspartic acid containing dicarboxylic acid and its application in
the enhancement of the thermal stability of chiral poly(amide-imide). RSC Adv
2014;4:42114-21.
[95] Zhang C, Yu J, Xu X, Sun Y. Effect of surface organic modified layered double
hydroxide on UV ageing resistance of bitumen. Petrol Sci Technol 2017;35:488-
94.
[96] Zhang Z, Qin J, Zhang W, Pan YT, Wang DY, Yang R. Synthesis of a novel dual
layered double hydroxide hybrid nanomaterial and its application in epoxy
nanocomposites. Chem Eng J 2020;381:122777.

76
 Journal Pre-proof

[97] Xie J, Wang H, Wang Z, Zhao Q, Yang Y, Waterhouse GI, et al. Innovative linear
low density polyethylene nanocomposite films reinforced with organophilic
layered double hydroxides: Fabrication, morphology and enhanced
multifunctional properties. Sci Rep 2018;8:52.
[98] Cao T, Feng Y, Chen G, Guo CY. Effect of photofunctional organo anion-
intercalated layered double hydroxide nanoparticles on poly(ethylene
terephthalate) nonisothermal crystallization kinetics. React Function Polym
2014;83:1-6.
[99] Deng F, Zhou H, Chen J, Huang H, Tian J, Huang Q, et al. Surface modification of
fluorescent Tb3+-doped layered double hydroxides with hyperbranched polymers
through host-guest interaction. Mater Sci Eng C 2019;104:109976.
[100] Martos A, Herrero M, Várez A, Levenfeld B. Synthesis and characterization of
new membranes based on sulfonated polysulfone/Zn,Al-heptamolibdate LDH.
Mater Lett 2015;152:125-7.
[101] Cai J, Heng HM, Hu XP, Xu QK, Miao F. A facile method for the preparation of

of
novel fire-retardant layered double hydroxide and its application as nanofiller in
UP. Polym Degrad Stab 2016;126:47-57.

ro
[102] Han Y, Wu Y, Shen M, Li T, Wang Y, Zhang Q, et al. Preparation and flame
retardancy of polystyrene nanocomposites based on layered double hydroxides.
Polym Comp 2015;38:1680-8.
-p
[103] Kalali EN, Wang X, Wang D-Y. Synthesis of a Fe3O4 nanosphere@Mg-Al
layered-double-hydroxide hybrid and application in the fabrication of
re
multifunctional epoxy nanocomposites. Ind Eng Chem Res 2016;55:6634-42.
[104] Zhang S, Tang W, Gu X, Jiang P, Sun J, Sophie D, et al. Flame retardancy and
thermal and mechanical performance of intercalated, layered double hydroxide
lP

composites of polyamide 11, aluminum phosphinate, and sulfamic acid. J Appl

Polym Sci 2016;133.
[105] Hu Z, Chen G. Novel nanocomposite hydrogels consisting of layered double
na

hydroxide with ultrahigh tensibility and hierarchical porous structure at low

inorganic content. Adv Mater 2014;26:5950-6.
[106] Labuschagne FJ, Molefe DM, Focke WW, van der Westhuizen I, Wright HC,
ur

Royeppen MD. Heat stabilising flexible PVC with layered double hydroxide
derivatives. Polym Degrad Stab 2015;113:46-54.
[107] Gómez-Fernández S, Ugarte L, Peña-Rodriguez C, Zubitur M, Corcuera MÁ,
Jo

Eceiza A. Flexible polyurethane foam nanocomposites with modified layered

double hydroxides. Appl Clay Sci 2016;123:109-20.
[108] Carja G, Kameshima Y, Nakajima A, Dranca C, Okada K. Nanosized silver-
anionic clay matrix as nanostructured ensembles with antimicrobial activity. Int J
Antimicrob Agents 2009;34:534-9.
[109] Gorrasi G, Bugatti V, Vittoria V. Pectins filled with LDH-antimicrobial
molecules: Preparation, characterization and physical properties. Carbohydr
Polym 2012;89:132-7.
[110] Nocchetti M, Donnadio A, Ambrogi V, Andreani P, Bastianini M, Pietrella D, et
al. Ag/AgCl nanoparticle decorated layered double hydroxides: synthesis,
characterization and antimicrobial properties. J Mater Chem B 2013;1:2383-93.
[111] Merchán M, Ouk TS, Kubát P, Lang K, Coelho C, Verney V, et al. Photostability
and photobactericidal properties of porphyrin-layered double hydroxide-
polyurethane composite films. J Mater Chem B 2013;1:2139-46.
[112] Mao L, Liu JY, Zheng SJ, Wu HQ, Liu YJ, Li ZH, et al. Mussel-inspired nano-
silver loaded layered double hydroxides embedded into a biodegradable polymer

77
 Journal Pre-proof

matrix for enhanced mechanical and gas barrier properties. RSC Adv
2019;9:5834-43.
[113] Mishra G, Dash B, Pandey S, Mohanty PP. Antibacterial actions of silver
nanoparticles incorporated Zn-Al layered double hydroxide and its spinel. J
Environ Chem Eng 2013;1:1124-30.
[114] El-Shahawy AA, El-Ela FIA, Mohamed NA, Eldine ZE, El Rouby WM.
Synthesis and evaluation of layered double hydroxide/doxycycline and cobalt
ferrite/chitosan nanohybrid efficacy on gram positive and gram negative bacteria.
Mater Sci Eng C 2018;91:361-71.
[115] Chen C, Gunawan P, Lou XWD, Xu R. Silver nanoparticles deposited layered
double hydroxide nanoporous coatings with excellent antimicrobial activities. Adv
Function Mater 2012;22:780-7.
[116] Yadollahi M, Namazi H, Aghazadeh M. Antibacterial carboxymethyl
cellulose/Ag nanocomposite hydrogels cross-linked with layered double
hydroxides. Int J Biol Macromol 2015;79:269-77.

of
[117] Allou N, Yadav A, Pal M, Goswamee RL. Biocompatible nanocomposite of
carboxymethyl cellulose and functionalized carbon-norfloxacin intercalated

ro
layered double hydroxides. Carbohydr Polym 2018;186:282-9.
[118] Xiao F, Liu X, Xiao Y, Chen F, Wu Y. A luminescent layered hybrid Ag-Ru/LDH
as a photocatalytic antibacterial agent. New J Chem 2017;41:7260-6.
-p
[119] Mallakpour S, Hatami M. Green and eco-friendly route for the synthesis of
Ag@Vitamin B9-LDH hybrid and its chitosan nanocomposites: Characterization
re
and antibacterial activity. Polymer 2018;154:188-99.
[120] Zhao S, Meng Z, Fan X, Jing R, Yang J, Shao Y, et al. Removal of heavy metals
from soil by vermiculite supported layered double hydroxides with three-
lP

dimensional hierarchical structure. Chem Eng J 2020;390:124554.

[121] Tang S, Yao Y, Chen T, Kong D, Shen W, Lee HK. Recent advances in the
application of layered double hydroxides in analytical chemistry: A review. Anal
na

Chim Acta 2020;1103:32-48.

[122] Rasool K, Pandey RP, Rasheed PA, Buczek S, Gogotsi Y, Mahmoud KA. Water
treatment and environmental remediation applications of two-dimensional metal
ur

carbides (MXenes). Mater Today 2019;30:80-102.

[123] Asiabi H, Yamini Y, Shamsayei M, Tahmasebi E. Highly selective and efficient
removal and extraction of heavy metals by layered double hydroxides intercalated
Jo

with the diphenylamine-4-sulfonate: A comparative study. Chem Eng J

2017;323:212-23.
[124] Qin Q, Wang J, Zhou T, Zheng Q, Huang L, Zhang Y, et al. Impact of organic
interlayer anions on the CO2 adsorption performance of Mg-Al layered double
hydroxides derived mixed oxides. J Energy Chem 2017;26:346-53.
[125] Wang P, Yin L, Wang X, Zhao G, Yu S, Song G, et al. L-cysteine intercalated
layered double hydroxide for highly efficient capture of U(VI) from aqueous
solutions. J Environ Manag 2018;217:468-77.
[126] Wang F, Liu Q, Li R, Li Z, Zhang H, Liu L, et al. Selective adsorption of uranium
(VI) onto prismatic sulfides from aqueous solution. Colloids Surf A
2016;490:215-21.
[127] Ma S, Huang L, Ma L, Shim Y, Islam SM, Wang P, et al. Efficient uranium
capture by polysulfide/layered double hydroxide composites. J Amer Chem Soc
2015;137:3670-7.

78
 Journal Pre-proof

[128] Li Y, Bi HY, Jin YS. Facile preparation of rhamnolipid-layered double hydroxide

nanocomposite for simultaneous adsorption of p-cresol and copper ions from
water. Chem Eng J 2017;308:78-88.
[129] Mallakpour S, Hatami M. Biosafe organic diacid intercalated LDH/PVC
nanocomposites versus pure LDH and organic diacid intercalated LDH: Synthesis,
characterization and removal behaviour of Cd2+ from aqueous test solution. Appl
Clay Sci 2017;149:28-40.
[130] Zhang X, Dou Y, Gao C, He C, Gao J, Zhao S, et al. Removal of Cd(II) by
modified maifanite coated with Mg-layered double hydroxides in constructed
rapid infiltration systems. Sci Total Environ 2019;685:951-62.
[131] Shamsayei M, Yamini Y, Asiabi H. Fabrication of zwitterionic histidine/layered
double hydroxide hybrid nanosheets for highly efficient and fast removal of
anionic dyes. J Colloid Interface Sci 2018;529:255-64.
[132] Mohd Sidek HB, Jo YK, Kim TW, Hwang YK, Chang J-S, Hwang S-J.
Enhancement of the water adsorptivity of metal-organic frameworks upon

of
hybridization with layered double hydroxide nanosheets. The J Phys Chem C
2017;121:15008-16.

ro
[133] Dinari M, Haghighi A, Asadi P. Facile synthesis of ZnAl-EDTA layered double
hydroxide/poly(vinyl alcohol) nanocomposites as an efficient adsorbent of Cd(II)
ions from the aqueous solution. Appl Clay Sci 2019;170:21-8.
-p
[134] Duan S, Ma W, Cheng Z, Zong P, Sha X, Meng F. Preparation of modified Mg/Al
layered double hydroxide in saccharide system and its application to remove
re
As(V) from glucose solution. Colloids Surf A 2016;490:250-7.
[135] Zhou Q, Chen F, Wu W, Bu R, Li W, Yang F. Reactive orange 5 removal from
aqueous solution using hydroxyl ammonium ionic liquids/layered double
lP

hydroxides intercalation composites. Chem Eng J 2016;285:198-206.

[136] Mallakpour S, Behranvand V. Water sanitization by the elimination of Cd2+ Using
recycled PET/MWNT/LDH composite: Morphology, thermal, kinetic and
na

isotherm studies. ACS Sustain Chem Eng 2017;5:5746–57.

[137] Zouai F, Benabid FZ, Bouhelal S, Cagiao ME, Benachour D, Baltá Calleja FJ.
Nanostructure and morphology of poly(vinylidene fluoride)/polymethyl
ur

(methacrylate)/clay nanocomposites: correlation to micromechanical properties. J

Mater Sci 2017;52:4345-55.
[138] Mallakpour S, Hatami M. An effective, low-cost and recyclable bio-adsorbent
Jo

having amino acid intercalated LDH@ Fe3O4/PVA magnetic nanocomposites for

removal of methyl orange from aqueous solution. Appl Clay Sci 2019;174:127-
37.
[139] Wang J, Zhang L, Zhang T, Du T, Li T, Yue T, et al. Selective removal of heavy
metal ions in aqueous solutions by sulfide-selector intercalated layered double
hydroxide adsorbent. J Mater Sci Technol 2019;35:1809-16.
[140] Huang D, Liu C, Zhang C, Deng R, Wang R, Xue W, et al. Cr(VI) removal from
aqueous solution using biochar modified with Mg/Al-layered double hydroxide
intercalated with ethylenediaminetetraacetic acid. Biores Technol 2019;276:127-
32.
[141] Stimpfling T, Leroux F, Hintze-Bruening H. Unraveling EDTA corrosion
inhibition when interleaved into Layered Double Hydroxide epoxy filler system
coated onto aluminum AA 2024. Appl Clay Sci 2013;83:32-41.
[142] Stimpfling T, Leroux F, Hintze‐Bruening H. Phosphate‐based organic molecules
interleaved with layered double hydroxide: Unraveling the roles of host cations

79
 Journal Pre-proof

and the guest‐inhibiting effect in aluminum corrosion protection. Eur J Inorg

Chem 2012;2012:5396-404.
[143] Li J, Lin K, Luo X, Zhang H, Cheng YF, Li X, et al. Enhanced corrosion
protection property of Li-Al layered double hydroxides (LDHs) film modified by
2-guanidinosuccinic acid with excellent self-repairing and self-antibacterial
properties. Appl Surf Sci 2019;480:384-94.
[144] Mei Y, Xu J, Jiang L, Tan Q. Enhancing corrosion resistance of epoxy coating on
steel reinforcement by aminobenzoate intercalated layered double hydroxides.
Prog Org Coat 2019;134:288-96.
[145] Yao QS, Zhang F, Song L, Zeng RC, Cui LY, Li SQ, et al. Corrosion resistance of
a ceria/polymethyltrimethoxysilane modified Mg-Al-layered double hydroxide on
AZ31 magnesium alloy. J Alloys Comp 2018;764:913-28.
[146] Zeng RC, Li XT, Liu ZG, Zhang F, Li SQ, Cui HZ. Corrosion resistance of Zn-Al
layered double hydroxide/poly(lactic acid) composite coating on magnesium alloy
AZ31. Front Mater Sci 2015;9:355-65.

of
[147] Wang XT, Ning XB, Shao Q, Ge SS, Fei ZY, Lei J, et al. ZnFeAl-layered double
hydroxides/TiO2 composites as photoanodes for photocathodic protection of 304

ro
stainless steel. Sci Rep 2018;8:4116.
[148] Lin K, Luo X, Pan X, Zhang C, Liu Y. Enhanced corrosion resistance of LiAl-
layered double hydroxide (LDH) coating modified with a Schiff base salt on
-p
aluminum alloy by one step in-situ synthesis at low temperature. Appl Surf Sci
2019;463:1085-96.
re
[149] Tang Y, Wu F, Fang L, Guan T, Hu J, Zhang S. A comparative study and
optimization of corrosion resistance of ZnAl layered double hydroxides films
intercalated with different anions on AZ31 Mg alloys. Surf Coat Technol
lP

2019;358:594-603.
[150] Khan SB, Alamry KA, Alyahyawi NA, Asiri AM. Controlled release of organic-
inorganic nanohybrid: cefadroxil intercalated Zn-Al-layered double hydroxide. Int
na

J Nanomed 2018;13:3203.
[151] Santamaria CM, Woodruff A, Yang R, Kohane DS. Drug delivery systems for
prolonged duration local anesthesia. Mater Today 2017;20:22-31.
ur

[152] Cao Z, Adnan NNM, Wang G, Rawal A, Shi B, Liu R, et al. Enhanced colloidal
stability and protein resistance of layered double hydroxide nanoparticles with
phosphonic acid-terminated PEG coating for drug delivery. J Colloid Interface Sci
Jo

2018;521:242-51.
[153] Nath J, Dolui SK. Synthesis of carboxymethyl cellulose-g-poly(acrylic acid)/LDH
hydrogel for in vitro controlled release of vitamin B 12. Appl Clay Sci
2018;155:65-73.
[154] Valarezo E, Tammaro L, González S, Malagón O, Vittoria V. Fabrication and
sustained release properties of poly(ε-caprolactone) electrospun fibers loaded with
layered double hydroxide nanoparticles intercalated with amoxicillin. Appl Clay
Sci 2013;72:104-9.
[155] Xu J, Jiao Y, Shao X, Zhou C. Controlled dual release of hydrophobic and
hydrophilic drugs from electrospun poly(L-lactic acid) fiber mats loaded with
chitosan microspheres. Mater Lett 2011;65:2800-3.
[156] Kontogiannopoulos KN, Assimopoulou AN, Tsivintzelis I, Panayiotou C,
Papageorgiou VP. Electrospun fiber mats containing shikonin and derivatives
with potential biomedical applications. Int J Pharm 2011;409:216-28.

80
 Journal Pre-proof

[157] Mallakpour S, Hatami M. Fabrication and characterization of pH-sensitive bio-

nanocomposite beads havening folic acid intercalated LDH and chitosan: Drug
release and mechanism evaluation. Int J Biol Macromol 2019;122:157-67.
[158] San Román S, Almeida GN, del Arco M, Martín C. Dexketoprofen and
aceclofenac release from layered double hydroxide and SBA-15 ordered
mesoporous material. Appl Clay Sci 2016;121:9-16.
[159] Rojas R, Linck YG, Cuffini SL, Monti GA, Giacomelli CE. Structural and
physicochemical aspects of drug release from layered double hydroxides and
layered hydroxide salts. Appl Clay Sci 2015;109:119-26.
[160] Shahabadi N, Razlansari M, Zhaleh H, Mansouri K. Antiproliferative effects of
new magnetic pH-responsive drug delivery system composed of Fe3O4, CaAl
layered double hydroxide and levodopa on melanoma cancer cells. Mater Sci Eng
C 2019;101:472-86.
[161] Kang H, Kim HJ, Yang JH, Kim TH, Choi G, Paek SM, et al. Intracrystalline
structure and release pattern of ferulic acid intercalated into layered double

of
hydroxide through various synthesis routes. Appl Clay Sci 2015;112:32-9.
[162] Gao X, Lei L, O'Hare D, Xie J, Gao P, Chang T. Intercalation and controlled

ro
release properties of vitamin C intercalated layered double hydroxide. J Solid
State Chem 2013;203:174-80.
[163] Li X, Gong P, Li Y, Yu J, Wang F, Li X, et al. Double-carrier drug delivery
-p
system based on polyurethane-polyvinyl alcohol/layered double hydroxide
nanocomposite hydrogel. Mater Lett 2019;243:1-4.
re
[164] Barkhordari S, Yadollahi M. Carboxymethyl cellulose capsulated layered double
hydroxides/drug nanohybrids for Cephalexin oral delivery. Appl Clay Sci
2016;121-122:77-85.
lP

[165] Zuo H, Chen W, Cooper HM, Xu ZP. A facile way of modifying layered double
hydroxide nanoparticles with targeting ligand-conjugated albumin for enhanced
delivery to brain tumour cells. ACS Appl Mater Interfaces 2017;9:20444–53.
na

[166] Sarijo SH, Jadam ML, Md Saleh F. Intercalation of fenoprofen into layered
double hydroxide for the formation of controlled release anti-inflammatory drug.
Adv Mater Res 2019;1142:230-3.
ur

[167] Kerchiche S, Chebout R, Barama A, Bachari K. New way for iron introduction in
LDH matrix used as catalysts for Friedel-Crafts reactions. Arab J Chem
2017;10:S328-S33.
Jo

[168] Singha S, Sahoo M, Parida K. Highly active Pd nanoparticles dispersed on amine

functionalized layered double hydroxide for Suzuki coupling reaction. Dalton
Trans 2011;40:7130-2.
[169] Wen X, Li R, Yang Y, Chen J, Zhang F. An egg-shell type Ni/Al2O3 catalyst
derived from layered double hydroxides precursor for selective hydrogenation of
pyrolysis gasoline. Appl Cat A 2013;468:204-15.
[170] Sahoo M, Parida K. Pd(II) loaded on diamine functionalized LDH for oxidation of
primary alcohol using water as solvent. Appl Cat A 2013;460:36-45.
[171] Jia Y, Zhang L, Gao G, Chen H, Wang B, Zhou J, et al. A Heterostructure
coupling of exfoliated Ni-Fe hydroxide nanosheet and defective graphene as a
bifunctional electrocatalyst for overall water splitting. Adv Mater
2017;29:1700017.
[172] Shen Y, Yin K, An C, Xiao Z. Design of a difunctional Zn-Ti LDHs supported
PdAu catalyst for selective hydrogenation of phenylacetylene. Appl Surf Sci
2018;456:1-6.

81
 Journal Pre-proof

[173] Subramanian T, Dhakshinamoorthy A, Pitchumani K. Amino acid intercalated

layered double hydroxide catalyzed chemoselective methylation of phenols and
thiophenols with dimethyl carbonate. Tetrahedr Lett 2013;54:7167-70.
[174] Mori K, Taga T, Yamashita H. Isolated single-atomic Ru catalyst bound on a
layered double hydroxide for hydrogenation of CO2 to formic acid. ACS Cat
2017;7:3147-51.
[175] Morimoto K, Tamura K, Yamada H, Sato T, Suzuki M. Determination and
reduction of Fe(III) incorporated into Mg-Fe layered double hydroxide structures.
Appl Clay Sci 2016;121:71-6.
[176] Dinari M, Dadkhah F. Swift reduction of 4-nitrophenol by easy recoverable
magnetite-Ag/layered double hydroxide/starch bionanocomposite. Carbohydr
Polym 2020;228:115392.
[177] Zhang M, Yao Q, Guan W, Lu C, Lin J-M. Layered double hydroxide-supported
carbon dots as an efficient heterogeneous Fenton-like catalyst for generation of
hydroxyl radicals. The J Phys Chem C 2014;118:10441-7.

of
[178] Ganiyu SO, Le TXH, Bechelany M, Esposito G, van Hullebusch ED, Oturan MA,
et al. A hierarchical CoFe-layered double hydroxide modified carbon-felt cathode

ro
for heterogeneous electro-Fenton process. J Mater Chem A 2017;5:3655-66.
[179] Mignani A, Ballarin B, Giorgetti M, Scavetta E, Tonelli D, Boanini E, et al.
Heterostructure of Au nanoparticles NiAl layered double hydroxide:
-p
electrosynthesis, characterization, and electrocatalytic properties. The J Phys
Chem C 2013;117:16221-30.
re
[180] Huang Z, Wu P, Gong B, Lu Y, Zhu N, Hu Z. Preservation of Fe complexes into
layered double hydroxides improves the efficiency and the chemical stability of
Fe complexes used as heterogeneous photo-Fenton catalysts. Appl Surf Sci
lP

2013;286:371-8.
[181] Mallakpour S, Hatami M. LDH-VB9-TiO2 and LDH-VB9-TiO2/crosslinked PVA
nanocomposite prepared via facile and green technique and their photo-
na

degradation application for methylene blue dye under ultraviolet illumination.

Appl Clay Sci 2018;163:235-48.
[182] Gong C, Chen F, Yang Q, Luo K, Yao F, Wang S, et al. Heterogeneous activation
ur

of peroxymonosulfate by Fe-Co layered doubled hydroxide for efficient catalytic

degradation of Rhoadmine B. Chem Eng J 2017;321:222-32.
[183] Darie M, Seftel EM, Mertens M, Ciocarlan RG, Cool P, Carja G. Harvesting solar
Jo

light on a tandem of Pt or Pt-Ag nanoparticles on layered double hydroxides

photocatalysts for p-nitrophenol degradation in water. Appl Clay Sci
2019;182:105250.
[184] Guo Q, Zhang Q, Wang H, Liu Z, Zhao Z. Core-shell structured ZnO@Cu-Zn-Al
layered double hydroxides with enhanced photocatalytic efficiency for CO2
reduction. Cat Commun 2016;77:118-22.
[185] Phuong NTK, Beak MW, Huy BT, Lee YI. Adsorption and photodegradation
kinetics of herbicide 2,4,5-trichlorophenoxyacetic acid with MgFeTi layered
double hydroxides. Chemosphere 2016;146:51-9.
[186] Xia SJ, Liu FX, Ni ZM, Shi W, Xue JL, Qian PP. Ti-based layered double
hydroxides: efficient photocatalysts for azo dyes degradation under visible light.
Appl Cat B 2014;144:570-9.
[187] Li S, Wang L, Li Y, Zhang L, Wang A, Xiao N, et al. Novel photocatalyst
incorporating Ni-Co layered double hydroxides with P-doped CdS for enhancing
photocatalytic activity towards hydrogen evolution. Appl Cat B 2019;254:145-55.

82
 Journal Pre-proof

[188] Huang Z, Wu P, Lu Y, Wang X, Zhu N, Dang Z. Enhancement of photocatalytic

degradation of dimethyl phthalate with nano-TiO2 immobilized onto hydrophobic
layered double hydroxides: a mechanism study. J Hazard Mater 2013;246:70-8.
[189] Mohamed F, Abukhadra MR, Shaban M. 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 2018;640:352-63.
[190] Gilea D, Radu T, Muresanu M, Carja G. Plasmonic photocatalysts based on silver
nanoparticles-layered double hydroxides for efficient removal of toxic compounds
using solar light. Appl Surf Sci 2018;444:407-13.
[191] Moghanian A, Firoozi S, Tahriri M, Sedghi A. A comparative study on the in
vitro formation of hydroxyapatite, cytotoxicity and antibacterial activity of 58S
bioactive glass substituted by Li and Sr. Mater Sci Eng C 2018;91:349-60.
[192] Mallakpour S, Hatami M. Highly capable and cost-effective chitosan
nanocomposite films containing folic acid-functionalized layered double

of
hydroxide and their in vitro bioactivity performance. Mater Chem Phys
2020;250:123044.

ro
[193] Szcześ A, Hołysz L, Chibowski E. Synthesis of hydroxyapatite for biomedical
applications. Adv Colloid Interface Sci 2017;249:321-30.
[194] Rezvani Z, Akbari M. Surface modification of hydroxyapatite crystals by Mg-Al-
-p
CO3-layered double hydroxides in HA/Mg-Al-CO3–LDH nanocomposite. New J
Chem 2015;39:5189-96.
re
[195] Fayyazbakhsh F, Solati-Hashjin M, Keshtkar A, Shokrgozar MA, Dehghan MM,
Larijani B. Novel layered double hydroxides-hydroxyapatite/gelatin bone tissue
engineering scaffolds: Fabrication, characterization, and in vivo study. Mater Sci
lP

Eng C 2017;76:701-14.
[196] Chen R, Zhu C, Lu J, Xiao J, Lei Y, Yu Z. BiVO4/α-Fe2O3 catalytic degradation
of gaseous benzene: Preparation, characterization and photocatalytic properties.
na

Appl Surf Sci 2018;427:141-7.

[197] Liu G, Zhao Y, Yao R, Li N, Wang M, Ren H, et al. Realizing high performance
solar water oxidation for Ti-doped hematite nanoarrays by synergistic decoration
ur

with ultrathin cobalt-iron phosphate nanolayers. Chem Eng J 2019;355:49-57.

[198] Bai S, Chu H, Xiang X, Luo R, He J, Chen A. Fabricating of Fe2O3/BiVO4
heterojunction based photoanode modified with NiFe-LDH nanosheets for
Jo

efficient solar water splitting. Chem Eng J 2018;350:148-56.

[199] Foruzin LJ, Rezvani Z, Nejati K. Fabrication of TiO2@ZnAl-layered double
hydroxide based anode material for dye-sensitized solar cell. RSC Adv
2016;6:10912-8.
[200] Luo M, Cai Z, Wang C, Bi Y, Qian L, Hao Y, et al. Phosphorus oxoanion-
intercalated layered double hydroxides for high-performance oxygen evolution.
Nano Res 2017;10:1732-9.
[201] Mustafa E, Tahira A, Adam RE, Ibupoto ZH, Elhag S, Willander M, et al.
Efficient Ni-Fe layered double hydroxides/ZnO nanostructures for photochemical
water splitting. J Solid State Chem 2019;273:186-91.
[202] Zhou JJ, Li Q, Chen C, Li YL, Tao K, Han L. Co3O4@CoNi-LDH core/shell
nanosheet arrays for high-performance battery-type supercapacitors. Chem Eng J
2018;350:551-8.
[203] Si HY, Deng QX, Chen LC, Wang L, Liu XY, Wu WS, et al. Hierarchical
Graphdiyne@NiFe layered double hydroxide heterostructures as a bifunctional
electrocatalyst for overall water splitting. J Alloys Comp 2019;794:261-7.

83
 Journal Pre-proof

[204] Wang Q, Niu T, Wang L, Huang J, She H. NiFe layered double-hydroxide

nanoparticles for efficiently enhancing performance of BiVO4 photoanode in
photoelectrochemical water splitting. Chines J Cat 2018;39:613-8.
[205] Yu X, Liu J, Yin W, Wang T, Quan L, Ran Y, et al. Ultrathin NiMn-layered
double hydroxide nanosheets coupled with α-Fe2O3 nanorod arrays for
photoelectrochemical water splitting. Appl Surf Sci 2019;492:264-71.
[206] Chong R, Wang G, Du Y, Jia Y, Wang X, Li C, et al. Anion engineering of
exfoliated CoAl layered double hydroxides on hematite photoanode toward highly
efficient photoelectrochemical water splitting. Chem Eng J 2019;366:523-30.

of
ro
-p
re
lP
na
ur
Jo

84
 Journal Pre-proof

The authors don’t have any conflict of interest.

of
ro
-p
re
lP
na
ur
Jo

85
 Journal Pre-proof

Highlights

 Constructional aspects and properties of LDHs are comprehensively argued.

 The most important methods of modified LDH preparation are presented.

 Modified LDHs are characterized by different analyses such as XRD, FT-IR, and TEM.

 The recent applications and future challenges of modified LDHs are discussed.

of
ro
-p
re
lP
na
ur
Jo

86