Applied Clay Science 157 (2018) 267–273

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Applied Clay Science

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Research paper

SEM study of the surface morphology and chemical composition of the T

MgAl- and MgGa-layered hydroxides in different steps of platinum catalysts
Pt/Mg(Al, Ga)Ox synthesis
⁎,1
L.N. Stepanovaa, , O.B. Belskayaa, A.N. Salanovb, A.N. Serkovab, V.A. Likholobova
a
Institute of Hydrocarbons Processing SB RAS, Neftezavodskaya St., 54, 644040 Omsk, Russia
b
Boreskov Institute of Catalysis SB RAS, Pr. Acad. Lavrentieva, 5, 630090 Novosibirsk, Russia

A R T I C LE I N FO A B S T R A C T

Keywords: The surface morphology and chemical composition of the MgAl- and MgGa-layered hydroxides as supports
Layered double hydroxides precursors were studied by SEM and EDX in all steps of the platinum catalysts Pt/Mg(Ga, Al)Ox synthesis. The
Scanning electron microscopy study revealed a higher structural stability of Ga-containing samples in comparison with Al-containing analogs,
Energy dispersive X-ray spectroscopy which shows up as their morphological invariability during calcination, activation of layered double hydroxides,
Morphology
and anchoring of the metal complex. A similar Mg/M3+ ratio of metals estimated by both the volumetric method
and EDX confirms that a uniform distribution of metals in the support is retained during the catalyst synthesis;
this will ensure the specified adsorption and acid-base properties of Pt/MgAlOx and Pt/MgGaOx, which are the
promising catalytic systems for dehydrogenation of light and higher alkanes.

1. Introduction
Layered double hydroxides (LDH), or hydrotalcites, are a class of
inorganic compounds that have been studied intensively for several
decades (Daud et al., 2016; Li et al., 2015; Rives et al., 2014; Theiss
et al., 2016; Zúmreoglu-Karan and Ay, 2012). LDH are the layered
compounds with a general formula [M1-x2+Mx3+(OH)2](Am−)x/
2+
m·nH2O, where M and M3+ are the cations of metals having different
valences and close radii, x = M3+/(M2+ + M3+). Therewith, an excess
positive charge of the hydroxide layers, which is formed due to the
presence of different valence cations, is compensated by hydrated Аm−
anions filling the interlayer space (Evans and Slade, 2006). Hydro-
talcites are widely employed as adsorbents, anion exchangers, and
catalysts of organic reactions requiring the presence of basic sites; their
structural, textural, acid-base and anion-exchange properties are de-
termined to a great extent by the nature and ratio of metals in the layers
as well as by the amount and size of anions in the interlayer space (Fan
et al., 2014). The moderate basicity and the possibility of its deliberate
control by varying the cationic and anionic composition of LDH open up
ample opportunities for their application as the precursors of supports
for metal catalysts. Thus, a promising direction is the synthesis of pla-
tinum catalysts supported on the M1M2Ox mixed oxide, which is formed
upon calcination of LDH at 500–650 °C, for dehydrogenation of alkanes
(Belskaya et al., 2016a, 2016b, 2015; Galvita et al., 2010; Siddiqi et al.,
2010; Stepanova et al., 2016, 2013; Sun et al., 2010). The synthesis of
such catalysts is a multistage process commonly comprising the fol-
lowing steps (Belskaya et al., 2016a, 2016b): synthesis of the initial
LDH with the interlayer carbonate ions (LDH-CO3); calcination of LDH-
СО3 to obtain the mixed oxide; rehydration of the mixed oxide with
restoration of the layered structure to produce the “activated” LDH with
the dominant content of hydroxyl anions in the interlayer space of
(LDH-OH); introduction of the active component precursor in the in-
terlayer space via the exchange of ОН− anions for [PtCl6]2−; and
thermal treatment of [PtCl6]2−/LDH in the oxidizing and reducing at-
mosphere. The transformation of LDH-CO3 to LDH-OH extends the
synthesis process but is a necessary step because the optimized and
reproducible synthesis of the carbonate form of LDH gives a material
with low anion-exchange properties and weak basicity.
The surface morphology strongly determines the conditions of re-
agents adsorption and diffusion, and information on the surface layer
composition allows estimating stability of the properties of the support
upon its contact with a solution of the active component precursor and
under high-temperature treatments. The morphology and chemical
composition of the surface layer can be studied by scanning electron
microscopy (SEM) using an appropriate set of attachments.
The morphology of LDH was examined by SEM in several works

⁎
Corresponding author.
E-mail address: Lchem@yandex.ru (L.N. Stepanova).
1
Present address: Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Neftezavodskaya St., 54, 644040 Omsk, Russia.

https://doi.org/10.1016/j.clay.2018.03.003
Received 13 October 2017; Received in revised form 28 February 2018; Accepted 2 March 2018
Available online 09 March 2018
0169-1317/ © 2018 Elsevier B.V. All rights reserved.
L.N. Stepanova et al.
(Adelantado et al., 2003; Belskaya et al., 2011; Benito et al., 2006;
Faour et al., 2010; Hibino and Ohya, 2009; Ma et al., 2008; Wang et al.,
2012, 2011, 2010a, 2010b). The best studied systems are magnesiu-
m‑aluminum ones (MgAl-LDH), the analogs of a natural mineral hy-
drotalcite Mg6Al2CO3(OH)16·4H2O. Q. Wang et al. (2012) investigated
MgAl-LDH as adsorbents of CO2. The effect of various factors – cationic
and anionic composition, methods and conditions of the synthesis – on
the morphology of MgAl-LDH was studied. Conditions of the synthesis
were found to be the key factor in the formation of the LDH structure. It
was shown that LDH of different composition synthesized under similar
conditions have the identical morphology. Since LDH are commonly
synthesized by coprecipitation, the pH of the synthesis plays an im-
portant role and its value is usually equal or exceeds the pH of pre-
cipitation of the most soluble hydroxide. Therewith, different surface
structures can be formed depending on the difference between the
chosen pH of the synthesis and the point of zero charge (PZC, the pH
value at which the total charge is zero) of the produced LDH. When
these values are equal, LDH with the “rosette” morphology is formed.
“Rosettes” are represented by platelets overlapping each other in dif-
ferent directions. If LDH are synthesized by coprecipitation, the for-
mation of the primary particles is very fast, but their growth is slow due
to electroneutrality of the surface at pHsynth = pHPZC. As a result, the
particle growth occurs mostly along the (001) plane, where the surface
charge density is minimal, with the formation of the so-called “ro-
settes”. At a lower pH of the synthesis (6.5–9), the morphology of LDH
is similar to that of γ-AlOOH, which is an aggregate of primary nano-
particles. At a high pH (above 14), when pHPZC < pHsynth, the LDH
particles are formed rapidly but their further growth does not occur. In
the process, the particle surface has a negative charge, which weakens
its interaction with Al(OH)− or СО32− in the solution. This results in
the formation of a fine-grain material (Wang et al., 2012).
The synthesis of MgAl-LDH by the method based on carbamide
decomposition also produced compounds with the rosette-like mor-
phology. However, in distinction to hydrotalcites obtained by copreci-
pitation, the authors of (Hibino and Ohya, 2009; Wang et al., 2010a)
observed the formation of well crystallized hexagonal plate-shaped
particles with a non-uniform particle size (~500 μm). These platelets of
a few micrometer thickness were disordered and intermeshed with each
other. The formation of such aggregates was attributed to the features
of carbamide synthesis. At elevated pressure and temperature, NH3
formed by decomposition of carbamide was supposed to interact with
the hydroxyl groups of LDH layers. The evolved gas forms numerous
small bubbles, which ultimately results in the aggregation of platelets in
the gas-liquid interface. The proposed mechanism was verified by EDX
data, according to which the obtained particles contain Mg, Al, O and N
atoms. The synthesis of NiAl-LDH (Faour et al., 2010) by both the co-
precipitation in a strongly alkaline medium and the decomposition of
carbamide led to the formation of LDH with the rosette morphology
(sand rose). Hydrothermal treatment of the produced LDH (except
those synthesized with the use of carbamide) facilitated an increase in
the particle size due to agglomeration of smaller particles as a result of
partial dissolution–precipitation that occurred under hydrothermal
conditions.
In some cases, the morphology of hydrotalcites is affected not only
by the synthesis conditions but also by the nature of cations and anions
in the composition of LDH. According to (Siddiqi et al., 2010), in the
case of MgAl- and MgGa-LDH, rosettes can associate into spheres.
MgFe-LDH are characterized by the presence of flake-like particles with
the size of 150–200 nm and ca. 25 nm thickness. The morphology of
MgMn-LDH is represented by aggregates of nanoparticles with the size
up to 35 nm (Wang et al., 2010b). Variation of interlayer anions showed
that in a series of CO32−, HCO3−, SO42−, Cl− only the carbonate-
containing samples have the rosette morphology. The other samples
have the stone-like morphology (Wang et al., 2011). It should be noted
that the loose structure of rosettes promotes the formation of LDH-CO3
porosity, whereas hydrotalcites containing other anions do not have a
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Applied Clay Science 157 (2018) 267–273
developed pore structure (Belskaya et al., 2011; Wang et al., 2011).
In addition to the rosette morphology, MgAl-LDH can have also the
plate-like one. In this case, the particles in SEM images look like
overlapping oval or hexagonal platelets. MgAl-LDH with such mor-
phology can be produced with the use of carbamide under hydro-
thermal conditions at microwave radiation (Benito et al., 2006). The
use of carbamide as a precipitating agent facilitates a slow formation of
LDH particles since carbamide decomposes with the formation of a base
only at a certain temperature. An exposure of the system to microwave
radiation increases the rate of carbamide hydrolysis, thus promoting a
faster formation of LDH with a large number of small crystals of a
uniform size. The plate-like material was observed also for LDH of other
cationic composition, for example, Co2+Co3+-LDH (Ma et al., 2008).
Although the unique morphology of LDH attracts considerable interest,
SEM studies on the surface transformations of LDH-based supports
during the catalyst synthesis are quite scarce. There are virtually no
works where energy dispersive X-ray spectroscopy (EDX) was used for
simultaneous analysis of changes in the surface chemical composition.
However, EDX is employed for qualitative and quantitative analysis of
the surface composition of metals and alloys (Adelantado et al., 2003;
Suba et al., 1994; Winkler et al., 2007; Wu et al., 2012) as well as
disperse materials, such as zeolites (Auroux et al., 1983; Majhi et al.,
2015; Shoumkova and Stoyanova, 2013) and catalysts of various
composition (Bednarova et al., 2002; Paksoy et al., 2015).
The goal of the work was to elucidate the effect of different pro-
cesses (calcination, rehydration, and anionic exchange) in the synthesis
of Pt/MgAlOx and Pt/MgGaOx catalysts on the morphology and che-
mical composition of the support surface layer by means of scanning
electron microscopy and analytical potential of an energy dispersive
spectrometer. Since a highly uniform distribution of components in the
structure of the support material is considered as one of the most im-
portant characteristics of double hydroxides and the corresponding
mixed oxides, this study was aimed to reveal whether this advantage is
retained during multistep treatments. The selectivity of the target
products formation and electronic state of the active component depend
on the metals ratio in LDH. With increasing Mg/Al ratio the growth of
LDH basic properties occurs, which promotes to reduce of the propor-
tion of platinum is in an oxidized state. It is known that electron defi-
cient platinum particles have the ability to adsorb olefins more
strongly. This can cause of further dehydrogenation of that olefins and,
consequently, to reduce catalysts selectivity through the formation of
side products with greater number of carbon atoms in its composition
(Belskaya et al., 2015). The object of the study was the systems based
on MgAl- and MgGa-LDH. Our previous works demonstrated that pla-
tinum catalysts supported on magnesium-aluminum oxides, which are
obtained from the corresponding LDH, are promising catalytic systems
for dehydrogenation of light and higher alkanes (Belskaya et al., 2016a,
2016b, 2015; Stepanova et al., 2016, 2013). Partial or complete re-
placement of aluminum by gallium leads to modifying of the Pt active
sites properties expressed in increase of the activity of platinum cata-
lysts based on the Ga-containing LDH while maintaining high se-
lectivity in propane dehydrogenation. This is mainly explained by
suppression of the reactions of the hydrogenolysis of CeC bonds.
(Belskaya et al., 2016b). At the high temperature stage (350–450 °C) of
reduction PteGa interaction occurs, that allows to modify the disperse
and catalytic properties of platinum. The formation of bimetallic par-
ticles occurs with the participation of gallium atoms closest to platinum
(traditionally the content of platinum in the catalyst is 0.3 wt.%) and
does not significantly affect its surface concentration in the support.
2. Experimental procedures
2.1. Synthesis of LDH
MgAl- and MgGa-LDH with the molar ratio Mg/M3+ = 2 were
synthesized by coprecipitation (Miata, 1975). To this end, an aqueous
L.N. Stepanova et al.
solution containing a mixture of magnesium Mg(NO3)2 and aluminum
Al(NO3)3 (or gallium Ga(NO3)3) nitrates with the total concentration of
metals CMg+Al(Ga) = 1 mol/L was added dropwise to an aqueous solu-
tion of sodium carbonate (C = 1 mol/L). The synthesis was carried out
at constant pH = 10 ± 0.1 and temperature 60 ± 3 °C. The pH value
was maintained by adding a solution of sodium hydroxide NaOH
(С = 1 mol/L). After adding the entire solution of salts, the suspension
was aged at the synthesis temperature for 18 h and then washed with
distilled water to a neutral pH of rinsing water. After that, the pre-
cipitate was separated from the solution using a Shott filter. The sub-
sequent drying at 80 °C for 16 h resulted in the formation of LDH with
СО32− anions in the interlayer space, (MgAl – CO3 and MgGa-CO3).
The “activated” form of LDH, (MgAl- and MgGa-OH), with the
predominant content of OH– anions in the interlayer space was ob-
tained by calcination of the carbonate-containing LDH at 550 °C leading
to the MgAlOx and MgGaOx mixed oxide and its subsequent rehydration
in distilled water.
2.2. Deposition of the active component precursor [PtCl6]2−
The [PtCl6]2− complex was introduced in the interlayer space of
LDH by the anionic exchange of OH– ions in MgAl(Ga)-OH for
[PtCl6]2−. The adsorption was performed from an excess of Н2[PtCl6]
aqueous solution at the support to solution volume ratio of 1:25, room
temperature and atmospheric pressure for 60 min, and then the pre-
cipitate was separated from the solution by filtering. The MgAl(Ga)-
[PtCl6] system was obtained after drying in air for 12 h. To obtain the
oxide form of the Pt/MgAlOx and Pt/MgGaOx catalyst, the system with
the deposited platinum complex was calcined at 550 °C for 3 h. The
platinum content in the final catalyst was 1 wt.%.
The concentration of metals in aqueous solutions and solid samples
(after dissolution) was estimated by inductively coupled plasma atomic
emission spectroscopy on a Varian 710-ES system (determination of Mg
and Ga concentrations) and by atomic absorption spectroscopy on an
ААS 6300 Shimadzu instrument (determination of Al concentration).
2.3. X-ray diffraction analysis (XRD)
X-ray diffraction studies were carried out on a D8 Advance (Bruker)
diffractometer using parallel Cu-Kα radiation in the 2θ angular range
from 5 to 80°. The scanning step was 0.05°, and the signal integration
time was 5 s/step. The phase composition of samples was identified
using the International diffraction database ICDD PDF-2.
Fig. 1. Diffraction patterns of MgAl (a) and MgGa (b) systems: 1 – Mg(Al, Ga)-CO3, 2 – Mg(Al, Ga)Ox, 3 – Mg(Al, Ga)-OH, 4 – Mg(Al, Ga)-[PtCl6]. Mg(Al, Ga)-[PtCl6] was not calcined
before XRD recording.
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Applied Clay Science 157 (2018) 267–273
2.4. Scanning electron microscopy (SEM)
The surface morphology of layered double hydroxides and systems
with supported platinum complexes were investigated using scanning
electron microscopy on a JSM-6460 LV (JEOL) instrument with the
tungsten cathode and an accelerating voltage of 20 kV. Before each of
experiments, the samples were ground in an agate mortar and fixed on a
conducting double-sided carbon Scotch tape. To prevent the re-char-
ging effects, a conducting gold film was sputtered on the fixed samples.
Prior to each experiment, the samples were evacuated in the micro-
scope chamber for 15–20 min to remove volatile compounds from the
surface, which could exert a detrimental effect on the secondary elec-
tron emission and thus deteriorate quality of the image.
The qualitative and quantitative X-ray spectral microanalysis was
performed using a special analytical attachment of an energy dispersive
X-ray spectroscope INCA Energy-350 (Oxford Instruments) with an
energy resolution of 127.37 eV at 5.895 keV (Mn) for recording X-ray
quanta with an energy from 0.1 to 20 keV. The indicated spectrometer
makes it possible to identify all elements from Be4 to U92 at a minimum
content in the sample of ca. 0.1 wt%. The characteristic X-ray quanta
emitted upon interaction of the probe electrons with atoms of the
sample are recorded by the spectrometer to obtain a spectrum de-
monstrating the distribution of the amount of quanta versus their en-
ergy. Therewith, the chemical analysis can be made at certain points of
the surface and in selected regions. Among the main conditions of
quantitative X-ray spectral microanalysis is the use of samples with a
smooth surface. Since most of the studied materials do not possess a
perfectly smooth surface, this method is employed in a semiquantitative
mode. To examine the chemical composition, the powdered samples
were fixed on a conducting double-sided carbon Scotch tape, and a
carbon film was sputtered.
3. Results and discussion
To reveal changes in the surface morphology and chemical com-
position, MgAl- and MgGa-LDH with the ratio Mg/Al and Mg/Ga = 2
were synthesized. The systems were examined after consecutive pro-
cesses: calcination at 550 °C, rehydration, anionic exchange, and re-
calcination at 550 °C producing the oxide form of the final catalyst:
T = 550 °C H2 O
M(Al, Ga) − CO3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Mg(Al, Ga)Ox ⎯⎯⎯→ Mg(Al, Ga) − OH
[PtCl6]2 − T = 550 °C
⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Mg(Al, Ga) − [PtCl 6] ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Pt/Mg(Al Ga)Ox
According to XRD data, the synthesized MgAl- and MgGa-СО3 have
the hydrotalcite-like structure with a typical set of reflections (Evans
L.N. Stepanova et al.
and Slade, 2006) on the diffraction pattern (Fig. 1). Detailed in-
vestigation of cell parameters changes, occurring at different stages of
Pt/Mg(Al, Ga)Ox preparation, were studied in previous publications
[Belskaya et al., 2016b; Stepanova et al., 2017]. Calcination of carbo-
nate-containing LDH at the chosen temperature results in mixed oxide
formation and disappearance of reflections corresponding to the
layered structure and appearance of the bands typical of the layered
defect spinel (Leont'eva et al., 2012; Leont'eva et al., 2014), in which
the octahedral periclase layers alternate with the mixed tetra-
hedraloctahedral spinel layers with the ordered distribution of mag-
nesium and aluminum cations over octahedral and tetrahedral sites.
The layered defect spinel is closed to periclase (MgO), but has less cell
parameter a (4.177(1) Å) [Belskaya et al., 2013]. Rehydration of the
mixed oxides promoted to hydrotalcite-like structure restore with the
formation of «activated» form of LDH with preferential content of OH– -
anions in interlayer space («memory effect»). When CO32– - anions are
replaced by OH– - anions the broadening of reflexes at the diffracto-
grams occur. This can be explained by structural change which is ex-
pressed in an increase in the LDH layers disorder. The phases other than
hydrotalcite were not found at diffractograms. The conditions of the
anionic exchange proceeding in an acid medium did not lead to de-
struction of the hydrotalcite-like structure of MgAl-[PtCl6] and MgGa-
[PtCl6]. Corresponding diffraction patters are characterized by reten-
tion of the set of reflections typical for LDH.
3.1. A SEM study of the surface morphology
Fig. 2 displays SEM images of MgAl-LDH and MgGa-LDH with dif-
ferent anions (СО32−, ОН− and [PtCl6]2−) in the interlayer space, as
well as images of MgAlOx and MgGaOx (calcined Mg(Ga, Al)-CO3).
For both the MgAl-LDH and MgGa-LDH samples, changes in the
composition of interlayer space were accompanied by changes in the
surface morphology. The topography of carbonate- containing LDH is
represented by intermeshed rounded platelets, which are often ob-
served for hydrotalcites of such composition (Fig. 2 a, b).
Calcination of MgAl-LDH with the formation of MgAlOx mixed oxide
led to a pronounced coalescence of the platelets and formation of large
regions with a smooth surface (Fig. 2 c). Mixed magnesium‑gallium
oxide MgGaOx, on the contrary, retained the plate-like morphology
with a small increase in the platelet size (Fig. 2 d).
The replacement of СО32− anions by OH– upon rehydration pro-
duced changes in the LDH structure. These changes depend on the ca-
tionic composition of supports. Both samples showed changes in or-
ientation of platelets: the plate-like morphology transformed into the
rosette one (Fig. 2 e, f). The observed phenomenon can be attributed to
a higher PZC value for “activated” LDH (for example, PZC for MgAl-CO3
is ca. 9, and for MgAl-OH, 12), which results in reorientation of the
particles. However, for rehydrated MgAl-LDH (Fig. 2 e), the appearance
of additional non-layered regions of a regular shape was observed along
with the main phase of the layered hydroxide. As can be seen from the
Fig. 2 f, such non-layered regions are not observed for MgGa-OH. The
topography of gallium - containing LDH-OH is represented only by
rosette.
The anionic exchange of ОН− ions for [PtCl6]2− strongly affected
the surface morphology of MgAl-LDH (Fig. 2 g). Due to the interaction
of the support with an aqueous solution of chloroplatinic acid, the
“rosette” structure changed and became less pronounced, and the pla-
telet size decreased. In addition, particles with non-layered morphology
disappeared after recrystallization, and the material became phase-
homogeneous, which well agrees with the XRD data.
For MgGa-LDH with [PtCl6]2− anions the morphology of all regions
was represented by rosettes overlapping each other in different direc-
tions. This testifies to a higher structural stability of gallium-containing
samples. The exchange of interlayer carbonate-anions for OH– and
[PtCl6]2− increased the size of gallium-containing LDH platelets (Fig. 2
b, d, f, h).
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Applied Clay Science 157 (2018) 267–273
3.2. Investigation of chemical composition of the surface layer
EDX spectra of the samples were obtained from homogeneous
smooth regions with the size of ca. 6 μm2. The number of spectra for
each sample was no < 16. Correctness of the data obtained was con-
firmed by the agreement between amounts of elements in each of the
tested regions. EDX spectra of MgAl-CO3, MgAlOx and MgAl-OH sam-
ples show the bands corresponding to O, Mg and Al (the band of carbon
was present because carbon was sputtered on the samples before the
analysis), and the spectra of MgGa-CO3, MgGaOx and MgGa-OH have
the bands of O, Mg and Ga, respectively (Fig. 3). It should be noted that
the amount of oxygen in the calcined samples was lower than in non-
calcined ones due to removal of the oxygen-containing interlayer an-
ions and owing to dehydration and dehydroxylation of LDH layers ac-
companying the high-temperature treatment. According to EDX data,
for MgAl-OH non-layered regions are enriched with aluminum, because
their average content of metals is Mg = 14.7 at.% and Al = 10 at.%,
which correspond to the ratio Mg/Al = 1.5, whereas the other studied
regions of MgAl-OH have another content of metals: Mg = 17 at.% and
Al 8.5 at.%, and thus Mg/Al = 2.0. Previously it was found that for
MgAl-OH with Mg/Al > 3 additional peaks at 2θ = 14 and 22° are
occurred. These peaks refer to mixed layer phase [Leont'eva et al.,
2012]. Obviously the formation of mixed layer phase is already being
formed for LDH-OH with Mg/Al = 2. The absence of peaks for addi-
tional phase in the X-ray diffraction patterns can be explained by its
insignificant content (< 2 wt%) in the sample, or by XRD-amorphous of
this phase.
Upon introduction of the [PtCl6]2− anion in the interlayer space of
MgAl-LDH, the bands corresponding to chlorine appeared in the
spectra; and after calcination of the samples, platinum bands were
observed along with chlorine bands. It means that after calcination
platinum appears in the surface layer and becomes more accessible to
reagents. This is not accompanied by a complete removal of chlorine.
For gallium-containing samples, the bands corresponding to platinum
are observed both before and after calcination of the systems with the
supported metal complex. It is possibly, the higher concentration of
platinum complexes on the surface is characteristic for Ga-containing
samples. It's connected with stronger interaction of [PtCl6]2− with the
support of MgGa-system. Therefore Pt appears for this sample before
calcination.
In the synthesis of supported platinum catalysts, it is important to
preserve a homogeneous chemical composition of the support surface
before and after the deposition of the active component precursor. In
this connection, the ratio of metals Mg/Al and Mg/Ga in the surface
layer of samples was measured by EDX in all steps of the catalyst
synthesis. A comparison of the obtained data with the results of volu-
metric analysis (ICP-OES and AAS after a complete dissolution of the
sample) allows estimating the possible enrichment of the surface with
one of components of the support. Similar studies were carried out, for
example, to investigate the surface of steels (Einhauser, 1997) and
biosorption of metals (Michalak et al., 2011). As a result, the volumetric
method showed a higher accuracy and a lower detection limit of
components as compared to EDX. According to the data obtained in
these studies, EDX gave more comprehensive information on the com-
position of samples and detected S and Ti traces in the alloy, which
could not be made by the volumetric method. In distinction to the
averaged values obtained by the volumetric method, EDX revealed the
elemental composition of the sample surface, which may differ sub-
stantially in dependence on the morphology of selected regions.
According to the volumetric analysis, the ratio of metals in the
tested samples was Mg/Al = 2.0 and Mg/Ga = 2.2 (Table 1). A com-
parison of data obtained by different methods showed that EDX and
volumetric chemical analysis, which requires a complete dissolution of
samples, gave close ratios of metals for both the magnesium‑aluminum
and gallium‑magnesium samples. In addition, these values remained
virtually constant in all steps of the catalyst synthesis. As was indicated
L.N. Stepanova et al.
Fig. 2. SEM images of samples: a – MgAl-CO3, b – MgGa-CO3, c –MgAlOx, d – MgGaOx, e – MgAl-OH, f – MgGa-OH, g – MgAl-[PtCl6], h – MgGa-[PtCl6]. A ×30,000 magnification.
above, only the non-layered regions of a regular shape occurring in the
MgAl-OH sample were enriched with aluminum in comparison with
other regions and had the Mg/Al ratio of ~1.5.
Thus, a uniform distribution of components in the support as well as
phase homogeneity of the samples are preserved during the multistep
synthesis of the catalyst based on Ga-containing LDH. Apparently, it
provides high modifying effect of gallium in Pt/MgGaOx catalysts, that
leads to their increased activity and selectivity as well as low deacti-
vation degree (Belskaya et al., 2016b). Therewith, the use of EDX for
studying the disperse particles of layered hydroxides and mixed oxides
was shown to be an efficient approach to rapid analysis of not only
qualitative but also quantitative composition.
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Applied Clay Science 157 (2018) 267–273
4. Conclusions
The potential of SEM and EDX for investigation of morphology and
quantitative chemical composition of the support surface of Pt/MgAlOx
and Pt/MgGaOx catalysts in all steps of the synthesis was demonstrated.
It was found that calcination, activation of LDHs and anchoring of the
metal complex exert a smaller effect on the morphology of MgGa sys-
tems as compared to MgAl ones. This testifies to a higher structural
stability of Ga-containing samples. A uniform distribution of metals in
the support was retained during the catalyst synthesis, which showed
up as a similar ratio of metals Mg/M3+, which was estimated by both
the volumetric analysis and the surface EDX method. The revealed
properties of LDH-based Mg(Al, Ga) systems will ensure the desired
adsorption and acid-base properties of the catalysts.
L.N. Stepanova et al. Applied Clay Science 157 (2018) 267–273

Fig. 3. EDX analysis of the samples: a – MgAl-CO3, b – MgGa-CO3, c – MgAl-[PtCl6], d – MgGa-[PtCl6], e – MgAl-Pt, f – MgGa-Pt.

Table 1 Belskaya, O.B., Leont'eva, N.N., Gulyaeva, T.I., Drozdov, V.A., Doronin, V.P., Zaikovskii,
Mg/M3+ ratio calculated from volumetric and energy dispersive analysis. The platinum V.I., Likholobov, V.A., 2011. Formation of platinum sites on layered double hydro-
content in the final catalyst was 1.0 wt.%. xides type basic supports: I. Effect of the nature of the interlayer anion on the
structure characteristics of the layered aluminum–magnesium hydroxide and the
Sample Mg/Al Sample Mg/Ga formation of an oxide phase. Kinet. Catal. 52 (5), 761–769.
Belskaya, O.B., Leont'eva, N.N., Gulyaeva, T.I., Cherepanova, S.V., Talzi, V.P., Drozdov,
V.A., Likholobov, V.A., 2013. Influence of a doubly charged cation nature on the
Volumetric EDX Volumetric EDX
formation and properties of mixed oxides MAlOx (M = Mg2+, Zn2+, Ni2+) obtained
method method
from the layered hydroxide precursors. Russ. Chem. Bull. 62 (11), 2349–2361
International Edition. 5.
MgAl-CO3 2.0⁎ 2.1 MgGa-CO3 2.2a 2.4 Belskaya, O.B., Stepanova, L.N., Gulyaeva, T.I., Golinskii, D.V., Belyi, A.S., Likholobov,
MgAlOx 2.0 2.0 MgGaOx 2.2 2.4 V.A., 2015. Study of Pt/MgAlOx catalysts in n-decane dehydrogenation. Kinet. Catal.
MgAl-OH 2.0⁎ 2.0 MgGa-OH 2.2a 2.3 56 (5), 655–662.
MgAl-[PtCl6] – 2.4 MgGa- – 2.3 Belskaya, O.B., Stepanova, L.N., Gulyaeva, T.I., Erenburg, S.B., Trubina, S.V., Kvashnina,
[PtCl6] K., Nizovskii, A.I., Kalinkin, A.V., Zaikovskii, V.I., Bukhtiyarov, V.I., Likholobov,
MgAlPt – 2.1 MgGaPt – 2.5 V.A., 2016a. Zinc influence on the formation and properties of Pt/Mg(Zn)AlOx cat-
alysts synthesized from layered hydroxides. J. Catal. 341, 13–23.
a
The Mg/M3+ ratio in the samples was estimated after their calcination at 550 °C. Belskaya, O.B., Stepanova, L.N., Gulyaeva, T.I., Leont'eva, N.N., Zaikovskii, V.I., Salanov,
A.N., Likholobov, V.A., 2016b. Synthesis of Mg2+-, Al3+-, and Ga3+-containing
layered hydroxides and supported platinum catalysts based thereon. Kinet. Catal. 57
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