Solid State Sciences 63 (2017) 93e102

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Solid State Sciences

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Synthesis and Characterization of Layered Double Hydroxides

Containing Optically Active Transition Metal Ion
S.B. Tyagi a, Aneeta Kharkwal a, Nitu a, Mamta Kharkwal a, *, Raghunandan Sharma b
a
Department of Chemistry, Swami Shraddhanand College, University of Delhi, New Delhi 110036, India
b
Materials Science Programme, Indian Institute of Technology Kanpur, Kanpur 208016, India

a r t i c l e i n f o a b s t r a c t

Article history: The acetate intercalated layered double hydroxides of Zn and Mn, have been synthesized by chimie
Received 20 August 2016 douce method. The materials were characterized by XRD, TGA, CHN, IR, XPS, SEM-EDX and UV-visible
Received in revised form spectroscopy. The photoluminescence properties was also studied. The optical properties of layered
16 November 2016
hydroxides are active transition metal ion dependent, particularly d1
10 system plays an important role.
Accepted 18 November 2016
Available online 20 November 2016
Simultaneously the role of host e guest orientation has been considered the basis of photoluminescence.
Acetate ion can be exchanged with iodide and sulphate ions. The decomposed product resulted the pure
phase Mn doped zinc oxide are also reported.
Keywords:
Layered double hydroxides
© 2016 Elsevier Masson SAS. All rights reserved.
Intercalation
Ion exchange
Photoluminescence

1. Introduction
Layered materials have always been the materials of interest to
the researchers because of their ability to intercalate and exchange
ions into the layered structure. An attractive feature of these
layered compounds is that these can serve as a suitable template for
the exchange of various species in the interlayers. This includes
layered transition metal oxides, layered perovskites, layered double
hydroxides, hydroxy double salts etc. Here the intercalation in the
host material leads to ordered assemblies and the structures can be
controlled by host-guest interactions. This results in many inter-
esting properties such as catalysts, electrodes etc. [1e5]. The most
common in the latter category are the layered double hydroxide
(LDH) family of materials [6e10].
They are a class of ionic lamellar solids with positively charged
layers with two kinds of metallic cations and hydrated anions that
are exchangeable. The electric charge of the layers and the inter-
layer ions is just the opposite of that found in silicate clays (cationic
clays). These are also known as hydrotalcite-like compounds in the
name of the polytypes of the corresponding [Mg-Al] based mineral.
The general chemical composition is [MII1-xMIIIx (OH)2]An-x/
II
n.mH2O, where M (M ¼ Mg, Fe, Co, Cu, Ni, Mn or Zn) and M
* Corresponding author.
E-mail address: mamtakhar@gmail.com (M. Kharkwal).
(M ¼ Al, Cr, Ga, Mn or Fe) where MII and MIII are respectively
divalent and trivalent cations. The value of the coefficient x is equal
to the molar ratio MIII/(MII þ MIII) and is generally in the range
0.2e0.33 and An
is an anion with charge n. Structurally, the metal
octahedra share edges to form two dimensional infinite sheets with
a very similar structure to that of brucite [Mg(OH)2], with the
partial substitution of MII cations by MIII cations leading to a posi-
tive charge on the brucite layers. The layers stack to build a three
dimensional network with the positive charge being balanced by
anions arranged in hydrated interlayer galleries The remaining free
space of the interlayer is occupied by water of crystallization [11].
LDHs are functional materials as their composition is very
flexible. The divalent and trivalent cations, their atomic ratios and
the interlayer anions can be varied and this variation does not alter
the basic structure of the material. Thus, layered double hydroxides
(LDHs) are one of the most useful classes of inorganic compounds
that have been widely investigated for their rich intercalation
chemistry and for a wide variety of applications such as catalysis,
absorption/separation, additives in polymers, antacids, medicine,
and the immobilization of biological compounds and in environ-
mental remediation [12e28].
III
For example, the intercalation of biological species and organic
compounds between the layers has been investigated for their
possible use in diverse fields such as drug delivery carriers, sensing
devices, etc. LDHs have been used as additives for the removal of
sulfur oxides (SOx) in petroleum refining industries. LDHs have also

http://dx.doi.org/10.1016/j.solidstatesciences.2016.11.012
1293-2558/© 2016 Elsevier Masson SAS. All rights reserved.
94 S.B. Tyagi et al. / Solid State Sciences 63 (2017) 93e102

been successfully tested in the removal of pollutants, such as the

herbicide 2,4-dichlorophenoxiacetic acid (2,4-D), from aqueous
solutions. Furthermore, Mg-Zn-Al LDHs were demonstrated to
photo catalytically degrade 2,4-D and phenol. Other scientific and
technological applications of LDHs, worth mentioning are hybrid
composites, flame retardants and PVC additives [29e32]. New areas
have also been investigated for applications in the field of thin
films, conducting materials, electrodes and corrosion protection. In
addition, these materials were also tried as inorganic additives in
the development of new nano composites and nano hybrids
[33e37].
There are wide varieties of methods that are available for the
synthesis of layered double hydroxides. Traditionally, they are
synthesized by the co-precipitation of metallic salts with a
concentrated alkaline solution. Depending on the intended appli-
cation, several alternative methods have been employed such as
solegel method, urea hydrolysis method, ion-exchange method,
hydrothermal methods, intercalation method involving dissolution
Fig. 1. Powder X-ray diffraction patterns of layered hydroxide containing Zn and Mn
and re-coprecipitation procedure, salt-oxide (or hydroxide) ions, inset shows the Le-Bail fit of the PXRD.
method and template synthesis [38e49].
In the present work, novel layered hydroxy compound were
synthesized by chimie douce method (soft chemical method) in 3. Results and discussion
which the M2þ was Zn2þ and M3þ was Mn a spectroscopically active
1st row transition metal ion using H2O2 as the oxidant in the Fig. 1 shows the powder XRD pattern of the as-prepared Zn-Mn
absence and presence of a base. The associated optical properties hydroxides. The (00l) Bragg peaks can commonly be observed for
were also investigated. This combination is chosen for the reasons the synthesized materials, emphasising the formation of layered
that Zn2þ is a ‘d10’ system and therefore optical properties exhibited structure and indexed to a monoclinic cell. The cell parameters,
by such layered hydroxy compounds could essentially arise from a ¼ 10.305 (3)A , b ¼ 8.911 (2)A , c ¼ 16.141 (2)A , b ¼ 96.68 (2)
dopant ions. (space group: p21/n) were observed by Le-Bail fit of the powder X-
ray diffraction pattern (inset of Fig. 1). Bayerite like LDH having a
monoclinic symmetry derived from the structure of the mineral
nickelalumite in which charge compensation takes place by the
2. Experimental section incorporation of acetate ions in the interlayer region. Structural
refinement data very well matched with the reported polytype 2M2
For the synthesis Zn(CH3CO2)2.2H2O (99.5%, Merk) and [50]. The broading of peaks in a PXRD pattern is due to structural
Mn(CH3CO2)2 (99% Merk) were used as starting materials. Both the disorder. In layered materials structural disorder can arise due to
salt were taken in 3:1, and then added to a mixture of 5 ml of 30% interstratification and turbostratic disorder [51]. In addition to
H2O2 as an oxidant and 50 ml of deionized water. The prepared symmetry considerations, pH has an important role in polytype
solution was stirred for ½ h this resulted in a suspension with selection. In basic medium the compound is well defined in layered
foams. The suspension was stirred for 12 h without using the base structure and confirmed the formation of layered double hydrox-
and then dried at 60  C in an oven resulted a dirty white powder ides. LDH obtained at pH 10 (Fig. 2) shows only four peaks. The low
(2A). Same process also used to prepare another sample (2C) but angle peaks are indexed to the basal reflections 003 and 006 which
increase the pH 10 using NaOH solution. convinced the layering of compound. The sharp and symmetric
The powder X-ray diffraction patterns of the samples were
recorded using Rigaku Miniflex-II X-ray diffractometer employing
Cu-Ka1 radiation. Thermogravimetric analyses (Perkin Elmer Dia-
mond TG/DTA) were performed from ambient temperature to
800  C at a heating rate of 5  C min
1. Diffuse reflectance spectra of
the samples were collected on Perkin- Elmer UV- Vis spectropho-
tometer Lambda-35 attached with an integrating sphere and using
BaSO4 as the reference. FT-IR spectra of the samples were recorded
using Perkin-Elmer FT-IR spectrometer model 2000 employing KBr
as dispersal medium. Carbon, hydrogen, nitrogen and sulfur anal-
ysis were carried out on a CHNSO (Elemental) Analyser Vario E L III
Element Analyser, elementar Analysensysteme GmbH. The SEM
micrograph and EDX measurements of the sample were performed
on a Hitachi S-3700 M machine. The photoluminescence mea-
surements were executed using Horiba Jobin Yuvon Fluoro log-
modular spectrofluorometer at room temperature employing CW
Xenon lamp source. . The X-ray photoelectron spectroscopy (XPS)
data were recorded by PHI 5000 (Versa Prob II, FEI Inc.) spec-
trometer. The transmission electron microscopy (TEM) images and
energy dispersive X-ray analysis (EDX) measurements were per-
formed on the Philips Tecnai G2 30 transmission electron micro- Fig. 2. Powder X-ray diffraction patterns of layered hydroxide containing Zn and Mn
scope operating at an accelerating voltage of 300 kV. ions, in basic medium.
 S.B. Tyagi et al. / Solid State Sciences 63 (2017) 93e102
peaks in the PXRD pattern is characteristic of a high degree of
crystallinity.
Fig. 3(a) and (b) shows the XPS analysis of synthesized com-
pounds. C 1s spectra of the samples 2A and 2C shown in Fig. 3(a)
consist of peaks centered at 283.8 and 287.6 eV, which can be
assigned respectively to C
C (sp3) O
C¼O bonds of CH3COO

[52,53]. O is spectrum of 2A (Fig. 3(a)) reveals the presence of four
components centered at binding energies of 529.3, 530.6, 531.5 and
533 eV. The peaks may be assigned to O¼C-O (529.3 eV) [54,55],
-OH group of Zn1-xMnx (OH)2 (530.6 eV) [56], Zn-O (531.5 eV) [56]
and chemisorbed of water (533 eV) [57,58]. Similarly, O 1s spectrum
of 2C consists of components corresponding to O¼C-O, -OH group
of Zn1-xMnx (OH)2, and Zn-O, along with the fourth component at
534.7 eV associated to the interlayer water of (CH3COO)2$nH2O. As
shown in Fig. 3(b), Zn 2p spectrum of 2A can be deconvoluted in
three components centered at binding energies of 1020.0, 1020.8
and 1022.2 eV, which could be assigned to ZnO, Zn1-xMnx (OH)2
[59] and Zn-O-Mn, as well as Zn-vacancy [60], respectively. On the
other hand, the Zn 2p spectrum of 2C consists of two components
associated to Zn-O, Zn1-xMnx (OH)2, where the component corre-
sponding to Zn-O-Mn and Zn-vacancy disappears due to low
Fig. 3. (a) & (b) XPS spectra of ZnMn LDH.
95
fraction of Zn1-xMnx (OH)2 as compared to that of Zn-O. Mn 2p XPS
spectra of 2A and 2C exhibit shown in Fig. 3(b) exhibit 2p3/2 and
2p1/2 components centered roughly at 640 and 651 eV. Peak asso-
ciated to each of the spin (3/2, ½) can be deconvoluted in two
components, revealing the Mn to be in two different oxidation
states. Although the reported binding energies for Mnþ2 and Mnþ3
are closely spaced [61], the separation between the first component
(lower binding energy: ~640 and ~652 eV) of 2p3/2 and 2p1/2 spin
states (2A: 12 eV; 2C: 11.7 eV) indicates the oxidation states of Mn
for it to be þ3. On the other hand, the other component entered at
~642 eV may be associated to Mnþ4 [61]. From the results of XPS it
supports the formation of layered double hydroxides. In the syn-
thesis of LDH we dried the sample at 60  C in a vacuum oven. In this
process may be very little amount of hydroxide transform to the
oxide, which could not be confirmed by the PXRD pattern may be
due to very low intensity but this is traceable through XPS. The
formation of such type of impurity does not affect the application
part of LDH. Wang etal reported a mechanism of lattice dehydration
between adjacent hydroxyl ions to explain the solid phase transi-
tion from Zn(OH)2 to ZnO on heating the sample at lower tem-
perature for longer time. According to them the surface of Zn(OH)2
96 S.B. Tyagi et al. / Solid State Sciences 63 (2017) 93e102
Fig. 3. (continued).
contains many dangling OH ions, which are energetically higher
than those in the bulk due to a lack of full coordination of the ions.
These OH ions, therefore, might dehydrate between adjacent ones
to increase coordination and form little amount of ZnO also [11].
The morphology, microstructure and chemical composition of
the layered hydroxides were revealed by scanning electron mi-
croscopy (SEM) and EDX analysis. Figs. 4 and 5 shows the SEM
images of the prepared layered hydroxides (2A and 2C respectively)
which showed the formation of layers with regular plate like
morphology suggesting that layered form of metal hydroxides. The
as-prepared metal hydroxides were subjected to elemental map-
ping by the EDX analysis which confirmed that, both the metals, Zn
and Mn were present (see Figs. 4 and 5).
In this article we demonstrated the additional characterisation
of sample 2A only. The CHNS analysis clearly revealed that the
content of the acetate anion per formula unit is ~2. The formula
suggested is Zn0$75Mn0$25(OH)2(CH3COO)2H2O. The thermal be-
haviours of the as-prepared materials were investigated with TGA.
As plotted in Fig. 6, the Zn0$75Mn0$25(OH)2(CH3COO)2H2O material
show considerable weight decrease in three steps In the low tem-
perature region of 30e100  C, corresponds to exchangeable water
in the interlayer and is removed isothermally at 100  C. The second
step till 200  C is due to the loss of nonexchangeable water from the
inter layer, this weight decrease is assigned as the removal of
surface-adsorbed water and co-intercalated water molecules.
Weight loss at 180e200  C corresponding to the dehydroxylation of
the hydroxide layer and the evaporation of the guest acetates
species. No noticeable weight change can be detected for
Zn0$75Mn0$25(OH)2(CH3COO)2H2O at above 400  C, supporting the
decomposition of layered hydroxide to metal oxide [62]. The
chemical bonding nature of the as-prepared Zn-Mn LDH was
investigated by FT-IR spectroscopy (Fig. 7). As prepared
materials exhibit an intense and broad peak at 3400 cm
1, which
originates from the stretching mode of hydrogen-bonded
hydroxyl groups in the host lattice. The acetate-form of
Zn0$75Mn0$25(OH)2(CH3COO)2H2O exhibits strong absorption due
to the interlayer acetate at 1380 cm
1 and a strong band of the
acetate group at 1570 cm
1, whereas strong peaks related to the
acetate group appear at 665 and 1026 cm
1. This result provides
strong evidence for the intercalation of acetate anions in the ma-
terials. The optical properties of layered hydroxide were studied by
the UV-Visible diffuse reflectance spectra (Fig. 8). The Zn-Mn LDH
 S.B. Tyagi et al. / Solid State Sciences 63 (2017) 93e102 97

Fig. 4. Scanning electron microscopy (SEM) image and EDX of layered hydroxide.

shows two sharp absorptions at 220 nm and 263 nm were present
and absorption extended towards the visible region as represented
in graph.
The luminescent properties depend on many factors like de-
fects, coordination species, oxidation state of metal ion etc. The
properties of the metal ion are influenced by the intercalated anion
also thus, the photo luminescent properties of the compound
depend many aspect one of them is metal ion. Generally the pho-
toluminescence is not shown by d10 system being a stable one,
while the atoms other than d10 are PL active. The absence of PL in
stable system (d10) may be due to the shape of d orbitals (taken as a
single orbit) is spherical, as the transition of electron is least
possible. But when such atoms are present as host e guest system
then may be possibility of PL. Simultaneously the atoms other than
d10 system shows high quality of PL. The literature reveals the fact
that mainly the work is focussed only on the effect of rare earths
interlocutions, the properties are intercalating centered. While here
the host is taken as basis of photoluminescence and the effect is
made as host centered by intercalating the other moiety. Fig. 9
shows the emission spectrum of Zn-Mn sample in which emis-
sion were observed at different excitation wave length. Due to the
parity-forbidden transition of 3d / 3d, Mn activated inorganic
materials show a broad PL band varying from deep green to far red.
The emission color of Mn is sensitive to its local environment. The
excitation at 280 nm gave rise to two emission bands, band at
362 nm and 384 nm due to the transitions of the Mn ion. At 380
excitation it shows emissions at 486 and 520 nm. Again two
emissions are found at 486 and 543 nm at excitation wavelength
400 nm which is due to the spin-allowed transition of 5Eg/ 5T2g.
The interlayer acetate ions can be exchanged by other anions. In
the following section we describe our results obtained after anionic
exchange, introducing different anions, such as sulphate (Fig. 10)
and iodide (Fig. 11). A variety of inorganic and organic anions can be
intercalated in the interlayer of layered hydroxides through anion
98 S.B. Tyagi et al. / Solid State Sciences 63 (2017) 93e102

Fig. 5. Scanning electron microscopy (SEM) image and EDX of layered hydroxide in basic medium.

exchange reactions because the anions and water molecule which
fill the interlayer space are labile. The potentials of introducing new
molecules in the interlayer region are responsible for a viewing
platform to tune its properties. Optically active molecules, drugs
and dyes are intercalated into the interlayer region to form mate-
rials with combined properties of host and guest species. In this
work ZnMn-acetate sample was subjected to exchange with iodide
and sulphate ions. The exchange was carried out for 72 h by stirring
the sample in solution containing six times molar excess of the
anions to be incorporated. The solution was filtered and the pre-
cipitate was washed with ample amounts of decarbonated water.
All precipitates were dried at 60  C for 12 h in an oven. Every anion
exchange was repeated thrice to obtain reliable data. A shift in the
d-spacing in the precursor and the products from the XRD data
(Figs. 10 and 11) indicates that exchange has occurred which also
supported by IR spectroscopy and CHN analysis. SO2
4 has Td
symmetry and only two IR active normal modes, n3 and n4, at 1105
and 613 cm-1, were present. The IR spectrum shows that the SO2
4
ion retains its Td symmetry, representing a weak interaction with
the host material. The LDHs are natural hosts for mineralization of a
variety of anionic pollutants. The result of ion exchange shows that
the bayerite-based LDHs have a noticeably different interlayer
chemistry as compared to the brucite-based LDHs, as they have a
strong affinity for tetrahedral ions such as SO2
2
2

4 , CrO4 , and MoO4 ,
and a poor affinity for CO2
3 ions. Coulombic interactions directive
that the LDH has a stronger affinity for the divalent anions as
compared to the monovalent ions. Due to turbostratic disorder with
unclear interlayer sites and positional disorder of the interlayer
atoms the intercalated anion is not capable of forming H-bonds
which result the metal hydroxide layereinterlayer bonding is
 Fig. 6. Thermogravimetric analysis of the layered hydroxide.

Fig. 9. Emission spectra of layered double hydroxide, under 280 nm (filled circles),
380 nm (half filled circles) and 400 nm (hollow circles) excitation wavelengths.

Fig. 7. IR spectra of the layered hydroxide.

Fig. 10. Powder X-ray diffraction pattern of (a) acetate intercalated ZnMn hydroxide
(b) After anion exchange with sulphate ions.

Fig. 8. UV-Visible diffuse reflectance spectra of the layered hydroxide.

Fig. 11. Powder X-ray diffraction pattern of (a) acetate intercalated ZnMn hydroxide (b)
After anion exchange with iodide ions.
100 S.B. Tyagi et al. / Solid State Sciences 63 (2017) 93e102
Fig. 12. Powder X-ray diffraction pattern of ZnO and Mn (~25%) doped ZnO.
significantly weakened. The poor layereinterlayer bonding in I
-
LDHs greatly reduces their stability. This renders the mineralization
of iodine by the LDH host incompetent. In conclusion, the poor
stability of I- intercalated LDHs is ascribed to the structural
disorder.
One significant use of layered hydroxides are synthesis of pure
phase metal oxides. Nano scale materials are attracting more
attention due to their fascinating properties making them with
enhanced properties associated to their bulk counterparts due to
Fig. 13. TEM images of Mn doped ZnO.
quantum confinement effect and large surface area. ZnO attracted a
lot of research interests due to its environmentally friendly, low
cost of synthesis, excellent opto-electronical properties and highly
favourable device fabrication. It has a wide band gap (3.37 ev) and
large excitonic binding energy of nearly 60 MeV [63]. A number of
efforts have already been made to explore the effect of doping other
transition elements on its electrical, optical and magnetic proper-
ties [64e66]. When transition metals are doped in ZnO host; they
increase the defect density in the host and enhance the emissions
which put forward transition metals as suitable candidates for
many useful properties. But the synthesis method of pure phase
doped zinc oxide is very few, so we attempt to synthesis such type
of doped semiconductors by decomposing layered hydroxides
prepared by simple low-temperature oxidation procedure. The Mn
doped zinc oxides were prepared by decomposing the layered
double hydroxides at 400  C for 5 h in muffle furnace. One of the
important achievements is synthesis of pure phase doped Zinc
oxides samples by heating as synthesized basic Zn-Mn hydroxide
compound. Fig. 12 shows the evolution of X-ray diffraction (XRD)
patterns of Mn-doped ZnO system. The XRD pattern show that the
sample were polycrystalline with a wurtzite structure (space group
P63mc) of ZnO. Signals arising from Mn oxides, or any Mn related
phases were not found, the formation of the hexagonal wurtzite
phase is clearly observed. No additional peaks can be detected there
by without the presence of any impurities and confirming the
formation of pure and single phase within the range of Mn doping
concentrations, i.e. ~25%. No further annealing is needed in this
method compared to conventional method, where annealing is
usually necessary to remove some remaining precursor residues of
the formed amorphous phase into crystalline phase. The estimated
crystallite size is in the range of 20e30 nm, in agreement with TEM
 S.B. Tyagi et al. / Solid State Sciences 63 (2017) 93e102
Fig. 14. EDX analysis of Mn doped ZnO.
analysis (Fig. 13). The EDX analysis conform the presence of Mn ions
(Fig. 14). The TEM images shows the triangular plate like
morphology of doped ZnO.
4. Conclusion
The layered hydroxides of Zn and Mn, optically active transition
metal ions with intercalating acetate ion have been successfully
synthesized and characterized. The investigation of associated op-
tical properties was also conducted to consider their importance.
Generally the photoluminescence is not shown by d10 system
because of the shape of orbitals which perhaps provides the least
possibility of transition of electrons. Simultaneously it has also been
observed that the atom other than d10 system shows PL. Primarily
the work is focussed only on the effect of intercalated PL active ions
whereas here the host is taken on the basis of photoluminescence
and the effect is made on host centered by intercalating the other
moiety. The intercalation chemistry by the ion exchange process
was also studied. The layered hydroxide were decomposed and
obtained as pure phase doped ZnO, which give a simple method to
synthesize pure phase mixed metal oxides. This provides and en-
hances the scope for further investigation on optical properties of
layered hydroxides as well as doped metal oxides.
Conflict of interests
The authors declare that there is no conflict of interests
regarding the publication of this paper.
Acknowledgment
One of the author M. Kharkwal expresses and acknowledges
gratitude to SERB, DST for awarding the young scientist project (No.
SR/FT/CS-89/2011).
101
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