nanomaterials

Article
Hydrothermal Synthesis and Gas Sensing of
Monoclinic MoO3 Nanosheets
Teodóra Nagyné-Kovács 1 , Levente Studnicka 1 , István Endre Lukács 2 , Krisztina László 3 ,
Pawel Pasierb 4 , Imre Miklós Szilágyi 1, * and György Pokol 1,5
1 Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics,
Műegyetem rakpart 3, H-1111 Budapest, Hungary; kovacs.teodora@mail.bme.hu (T.N.-K.);
studnickalevi@gmail.com (L.S.); pokol.gyorgy@ttk.mta.hu (G.P.)
2 Research Institute for Technical Physics and Materials Science, Eötvös Loránd Research Network,
Konkoly Thege M. út 29-33, H-1121 Budapest, Hungary; lukacs.istvan@energia.mta.hu
3 Department of Physical Chemistry and Materials Science, Budapest University of Technology
and Economics, Műegyetem rakpart 3, H-1111 Budapest, Hungary; klaszlo@mail.bme.hu
4 Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30,
30-059 Kraków, Poland; ppasierb@agh.edu.pl
5 Research Centre for Natural Sciences, Eötvös Loránd Research Network, Magyar tudósok körútja 2,
H-1117 Budapest, Hungary
* Correspondence: imre.szilagyi@mail.bme.hu




Received: 31 March 2020; Accepted: 27 April 2020; Published: 7 May 2020


Abstract: Effects of different reaction parameters in the hydrothermal synthesis of molybdenum

oxides (MoO3 ) were investigated and monoclinic (β-) MoO3 was prepared hydrothermally for the
first time. Various temperatures (90/210 ◦ C, and as a novelty 240 ◦ C) and durations (3/6 h) were
used. At 240 ◦ C, cetyltrimethylammonium bromide (CTAB) and CrCl3 additives were also tested.
Both the reaction temperatures and durations played a significant role in the formation of the products.
At 90 ◦ C, h-MoO3 was obtained, while at 240 ◦ C the orthorhombic (α-) MoO3 formed with hexagonal
rod-like and nanofibrous morphology, respectively. The phase transformation between these two
phases was observed at 210 ◦ C. At this temperature, the 3 h reaction time resulted in the mixture of
h- and α-MoO3 , but 6 h led to pure α-MoO3 . With CTAB the product was bare o-MoO3 , however,
when CrCl3 was applied, pure metastable m-MoO3 formed with the well-crystallized nanosheet
morphology. The gas sensing of the MoO3 polymorphs was tested to H2 , which was the first such
gas sensing study in the case of m-WO3 . Monoclinic MoO3 was found to be more sensitive in H2
sensing than o-MoO3 . This initial gas sensing study indicates that m-MoO3 has promising gas sensing
properties and this MoO3 polymorph is promising to be studied in detail in the future.

Keywords: hydrothermal; monoclinic MoO3 ; nanosheet; CrCl3 ; gas sensing

1. Introduction
Molybdenum oxides (MoO3 ) are considerable materials among molybdenum (Mo) compounds
due to their excellent physical and chemical properties. MoO3 is one of the most important starting
materials for other Mo compounds, such as for sodium molybdate, ammonium di- or heptamolybdate,
or the Mo metal itself. MoO3 is also used as a catalyst in the industrial production of acrylonitrile from
propylene and ammonia. However, the constant interest in nanomaterials has made also nano MoO3
attractive, which has been proven to be a promising candidate in many fields, e.g., (photo)catalysis,
gas sensing, electrochemical cells, or even in forensic science and photothermal therapy [1–13].
MoO3 has four allotropes, each composed of differently linked MoO6 octahedra, the position of
which determines phase stability. The most commonly studied MoO3 phases are the thermodynamically

Nanomaterials 2020, 10, 891; doi:10.3390/nano10050891 www.mdpi.com/journal/nanomaterials

Nanomaterials 2020, 10, 891 2 of 12

stable orthorhombic (o-) or α-MoO3 and metastable monoclinic (m-) or β-MoO3 . Both phases have
excellent physical and chemical properties such as refractive index, band gap, and mechanical hardness.
Further crystalline phases are the metastable high-pressure ε-MoO3 and the relatively more stable
hexagonal (h-) MoO3 [14–16].
In the case of o-MoO3 , octahedra are distorted and form bilayers, which build up the well-known
stratified structure. These planar bilayers are composed of chains of MoO6 octahedra sharing corners
and edges in the specified direction and are held together vertically by weak Van der Waals forces.
In contrast, the crystal lattice of the metastable m-MoO3 is similar to the cubic ReO3 , where not layered,
but 3D crystal structure forms due to the corner-sharing of distorted octahedra in the three directions.
The h-MoO3 phase is constructed by such chains in which octahedra are linked by their corners.
These chains connect in such a way to form a hexagonal structure with the typical 1D hexagonal and
trigonal channels. The hexagonal channels may contain small ions (e.g., alkali metal or ammonium
ions) or water molecules, similar to hexagonal WO3 [14–17].
There are several reports about the hydrothermal preparation of MoO3 , but mostly only o-
and h-MoO3 are synthetized. Although the synthesis of the m-MoO3 phase has been carried out
by many methods (spray pyrolysis, pulsed laser thin-layer deposition, molecular beam epitaxy,
o-MoO3 conversion, solution-phase reaction, etc.), it has not been prepared hydrothermally yet in
pure form, only as a part of a mixture of MoO3 polymorphs [18]. On the other hand, it would
be useful because the hydrothermal method is simple, does not use high temperatures (usually it
operates only between 100 and 250 ◦ C), results in highly crystalline, monodisperse products, and
metastable phases can be also synthetized by it. Based on the literature, the highest temperatures
used in experiments to prepare MoO3 are typically 200–210 ◦ C. However, it would be worth trying to
use higher reaction temperatures as well, considering how important a small change in the reaction
parameters can be during the hydrothermal synthesis in general, regarding the crystalline phase and
morphology of the products. Consequently, neither the different reaction times nor the role of CTAB
(cetyltrimethylammonium bromide) and CrCl3 additives have been studied yet at temperatures above
200–210 ◦ C in the hydrothermal synthesis of MoO3 . Furthermore, so far the gas sensing properties
mostly of o- and h-MoO3 were tested [10,19–30]. To the best of our knowledge, there is only one paper
reporting the gas sensing of m-MoO3 , where very brief gas sensing data are given using H2 O and CO2
as test gases [31].
In the present investigation, we studied different reaction parameters in the hydrothermal
synthesis of MoO3 , focusing on the changes in the obtained crystalline phases and morphologies.
We investigated the effect of reaction temperature at 90, 210, and 240 ◦ C (using as high as 240 ◦ C
for the first time), and duration applying 3 and 6 h reaction times. Finally, we tested CTAB and
CrCl3 additives for the first time at 240 ◦ C. We examined the crystalline phases and morphologies
by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The as-prepared
different MoO3 allotropes were further studied by energy dispersive X-ray spectroscopy (EDX)
and specific surface area measurements, moreover by Fourier transformed infrared (FT-IR), Raman,
and ultraviolet-visible (UV–Vis) spectroscopies. Their band gap energies were also determined and
their gas sensing properties were analyzed towards H2 .

2. Materials and Methods

2.1. Materials and Equipment

Ammonium heptamolybdate tetrahydrate (≥99.0%), hexadecyltrimethylammonium bromide
(≥96.0%), and chromium(III) chloride hexahydrate (≥98.0%) were purchased from Sigma-Aldrich
(Budapest, Hungary) and used as received. Concentrated HNO3 (65%) was ordered from Molar
Chemicals (Halásztelek, Hungary), while ethanol (96 V/V%) from WVR (Budapest, Hungary).
Ion exchanged water was used throughout the experiments.
Nanomaterials 2020, 10, 891 3 of 12

For the hydrothermal reactions a 45 mL stainless steel, Teflon-lined autoclave (4744, General
Purpose Vessel, Parr Instruments, Moline, IL, USA), and a Nabertherm (Lilienthal, Germany)
muffle-furnace (L9/11/B410) were used.

2.2. Hydrothermal Reactions

For every synthesis, 0.5 g of ammonium heptamolibdate (AHM) was dissolved in 25 mL of ion
exchanged water, and then 5 mL cc. HNO3 was added. To study the effect of various additives, 0.1 g of
CTAB or CrCl3 was also dissolved in the selected reactions. After stirring the solution for a couple of
minutes, it was transferred into the autoclave, which was put into the electric furnace at particular
temperatures and for different durations. After the hydrothermal treatment, the precipitates were
filtered and washed several times with water and ethanol. Finally, the samples were dried at 60 ◦ C
for 2 h.
The hydrothermal reactions and their conditions are listed in Table 1.

Table 1. Experimental conditions of the hydrothermal reaction between AHM and HNO3 .

Sample Additive T (◦ C) t (h)

MoO3 -1 - 90 3
MoO3 -2 - 90 6
MoO3 -3 - 210 3
MoO3 -4 - 210 6
MoO3 -5 - 240 3
MoO3 -6 - 240 6
MoO3 -7 CTAB 240 3
MoO3 -8 CTAB 240 6
MoO3 -9 CrCl3 240 3
MoO3 -10 CrCl3 240 6

2.3. Characterization
X-ray powder diffraction (XRD) measurements were carried out by a X’Pert Pro MPD diffractometer
(PANalytical, Almelo, Netherlands) with Cu Kα radiation (λ = 0.15418 nm). For studying the
morphology of the samples, a LEO 1540 XB electron microscope (Zeiss, Oberkochen, Germany)
was used, while energy-dispersive X-ray spectroscopy (EDX) analyses were performed using a JEOL
JSM 5500-LV instrument (JEOL, Tokyo, Japan). FT-IR spectra were recorded by a Perkin Elmer 2000
FT-IR spectrometer (Perkin Elmer, Boston, MA, USA) between 450 and 4000 cm−1 using KBr pellets
(1 mg sample/300 mg KBr). Raman spectra were taken by a Jobin Yvon LabRam spectrometer (Horiba,
Kyoto, Japan) equipped with an Olympus BX41 optical microscope (Olympus, Tokyo, Japan) using
a frequency-doubled Nd-YAG laser (532 nm), while for diffuse reflectance UV–Vis measurements,
a Jasco V-570 UV/ VIS/ NIR spectrometer (Jasco, Tokyo, Japan) was used. The band gaps of the
products were calculated based on the UV–Vis spectra using αhυ = A (hυ − Eg )n equation, where α, hυ,
A, and Eg are equal to the molar absorption coefficient, photon energy, general constant, and band
gap energy, respectively. The n depends on the type of the electron transition in the compound and
is 12 (direct allowed) for MoO3 . Using the Tauc-plot, which is plotting (αhυ)2 against hυ, and then
drawing a tangent line onto the linear range and extrapolating, the band gap energy can be determined.
The Kubelka-Munk function was used to approximate the value of A. The N2 adsorption was measured
at −196 ◦ C with a Nova2000e (Quantachrome) computer-controlled apparatus and the apparent surface
area (SBET) of the samples were calculated from the Brunauer–Emmett–Teller (BET) model [32].

2.4. Gas Sensing Tests

For the experiments, Al2 O3 ceramic sensor plates with interdigital platinum electrodes were used.
First, with the usage of gold paste gold strands were attached onto the electrodes. Then, the sensor plate
was affixed to the end of a vertical ceramic tube, and it was connected to a circuit, to which an electrical
Nanomaterials 2020, 10, 891 4 of 12

resistance meter (HP 34410A) was connected. The samples were suspended in one drop of ethanol in an
Nanomaterials
Eppendorf tube, 2020,
and 10, x FOR PEER
a small REVIEW
amount of the suspension was transferred to the electrode. For heating4 of 13 the

sensor chips during the gas sensing measurements, an online, temperature, and atmosphere controlled
and atmosphere controlled furnace was utilized, which hosted the interdigital electrodes mounted
furnace was utilized, which hosted the interdigital electrodes mounted on the vertical ceramic tube (see
on the vertical ceramic tube (see details in [33]). In the experiments, H2 gas with different
detailsconcentrations
in [33]). In the experiments, H2 gas with
(25000/830/2500/5000/7500 different
and 10000 ppm)concentrations
was used and the(25,000/830/2500/5000/7500
carrier gas was N2. After
and 10,000 ppm) was used and the carrier gas was N . After the temperature
the temperature was set, the gas mixture was introduced to the sample and the change
2 was set,
inthe gas mixture
the electrical
was introduced
resistance of the sensor material was detected. The electrical resistance was measured for 1 h at eachwas
to the sample and the change in the electrical resistance of the sensor material
detected. The electrical resistance was measured for 1 h at each concentration.
concentration.

3. Results and Discussion

3. Results and Discussion

3.1.ofRole
3.1. Role of Reaction
Reaction Temperature
Temperature andand Duration
Duration onon
thetheFormation
Formationof
of MoO
MoO33

BasedBased onXRD
on their their patterns,
XRD patterns,
MoOMoO 3-1 and MoO3-2 were identified as pure h-MoO3 (ICDD 065-
3 -1 and MoO3 -2 were identified as pure h-MoO3 (ICDD 065-0033,
0033, Figure 1a,b). Every reflection belonged
Figure 1a,b). Every reflection belonged to this phase to thisindicating
phase indicating
that nothat no contaminations
contaminations werewere
present.
present. MoO3-3, which were prepared ◦ at 210 °C for 3 h, was composed of the h- and o-MoO3 phase
MoO3 -3, which were prepared at 210 C for 3 h, was composed of the h- and o-MoO3 phase (ICDD
(ICDD 01-074-7909); however, the longer reaction duration, namely 6 h, resulted in pure o-MoO3
01-074-7909); however, the longer reaction duration, namely 6 h, resulted in pure o-MoO3 (Figure 1c,d).
(Figure 1c,d). As the temperature was further increased to 240 °C, at both reaction times pure o-MoO3
◦ C, at both reaction times pure o-MoO was obtained
As thewas
temperature was further
obtained (Figure increased
1e,f). All samples to 240crystalline,
were 3
demonstrated by the sharp, intensive peaks.
(Figure 1e,f). All samples were crystalline, demonstrated by the sharp, intensive peaks.

Figure 1. XRD patterns of the samples synthetized in the hydrothermal reaction of AHM and HNO3
Figure 1. XRD patterns of the samples synthetized in the hydrothermal reaction of AHM and HNO3
at different temperatures and durations, (a) MoO3 -1 (90 ◦ C, 3 h), (b) MoO3 -2 (90 ◦ C, 6 h), (c) MoO3 -3
at different temperatures and durations, (a) MoO3-1 (90 °C, 3 h), (b) MoO3-2 (90 °C, 6 h), (c) MoO3-3
(210 ◦ C, 3 h), (d) MoO3 -4 (210 ◦ C, 6 h), (e) MoO3 -5 (240 ◦ C, 3 h), (f) MoO3 -6 (90 ◦ C, 3 h).
(210 °C, 3 h), (d) MoO3-4 (210 °C, 6 h), (e) MoO3-5 (240 °C, 3 h), (f) MoO3-6 (90 °C, 3 h).

According to SEM images, ◦ C were crystallized in a

According to SEM images,thethe h-MoO phasesprepared
h-MoO33 phases prepared at 90at°C90were crystallized in a well-
well-distinguished
distinguished hexagonal
hexagonal form formatatboth
bothreaction
reactiondurations
durations (Figure
(Figure 2, 2, MoO
MoO 3 -1-2).
3-1-2). TheTherodsrods
had had
a a
diameter of 7–12
diameter 7–12when
ofµm μm when a 3 h aduration was was
3 h duration applied, andand
applied, 8–188–18µmμm diameter
diameterwith a 6a h6 reaction
with h reactiontime;
however, their
time; lengththeir
however, was length
10–50 µm wasin bothμm
10–50 cases. It can
in both be also
cases. observed
It can be also that the MoO
observed -2 sample
that 3the MoO3-2had
a muchsample had asurface
smoother much smoother
and sharp surface
edges andduesharp edges
to the due to
longer the longer
reaction reaction time.
time.
In theIn the of
case case
MoO of MoO 3-3, the sample contained both h- and o-MoO3 phases, whose presence was
3 -3, the sample contained both h- and o-MoO3 phases, whose presence was
obvious based on the observed
obvious based on the observed morphologies. morphologies.InInaddition
addition to to the
the robust
robusthexagonal
hexagonal rods,
rods,200–500
200–500nm nm
thick fibers formed, with longer (30–50 μm) lengths (in some cases they were broken into shorter, i.e.,
thick fibers formed, with longer (30–50 µm) lengths (in some cases they were broken into shorter, i.e.,
1–2 μm pieces), referring to the o-MoO3 phase (Figure 2, MoO3-3). The morphology of MoO3-4 was,
1–2 µm pieces), referring to the o-MoO3 phase (Figure 2, MoO3 -3). The morphology of MoO3 -4 was,
however, homogenous, and the sample was composed of 250–800 nm thick and 10–50 μm long fibers
however, homogenous,
owing to the presence andofthe onlysample was3 composed
the o-MoO phase (Figure of 2,
250–800
MoO3-4). nm thick and 10–50 µm long fibers
owing to theWhenpresence of only
increasing the the o-MoO3 to
temperature phase (Figure
240 °C, both 2, MoO3durations
reaction -4). resulted in o-MoO3 with
When increasing theThe temperature ◦
fibrous morphology. diameter of to
the240
fibersC,was
both reaction
250–800 durations
nm when resulted
3 h was applied,in buto-MoO 3 with
the fibers
fibrousbecame
morphology.
500–1000The nmdiameter
thick withof6 the fibers time.
h reaction was 250–800
Their lengthnm when 3 h was
was several applied,
10–50 μm in butboththe fibers
cases
(Figure 2, MoO -5-6).
became 500–1000 nm thick with 6 h reaction time. Their length was several 10–50 µm in both cases
3

(Figure 2, MoO3 -5-6).

Nanomaterials 2020, 10, 891 5 of 12
Nanomaterials 2020, 10, x FOR PEER REVIEW 5 of 13

Figure 2. SEM
2. SEM images
images of the
of the samplessynthetized
samples synthetized in
in the
the hydrothermal
hydrothermal reaction of AHM
reaction andand
of AHM HNO 3 at
HNO
Figure 3 at
different temperatures and durations, MoO3-1 90 ◦°C, 3 h, MoO3-2: 90 °C,◦ 6 h, MoO3-3: 210 °C, 3 ◦h,
different temperatures and durations, MoO3 -1 90 C, 3 h, MoO3 -2: 90 C, 6 h, MoO3 -3: 210 C, 3 h,
MoO3-4: 210 °C, 6 h, MoO3-5: 240 °C, 3 h, MoO3-6: 240 °C, 6 h.
MoO3 -4: 210 ◦ C, 6 h, MoO3 -5: 240 ◦ C, 3 h, MoO3 -6: 240 ◦ C, 6 h.
Based on these results, it was found that the crystalline structure and morphology of the
Based on these results, it was found that the crystalline structure and morphology of the obtained
obtained products can be easily influenced by the appropriate choice of reaction temperature and
products can be easily influenced by the appropriate choice of reaction temperature and duration.
duration. The lower temperature of 90 °C resulted in a pure hexagonal MoO3 structure with the
The lower temperature ◦ C resulted in a pure hexagonal MoO structure with the characteristic
of 90micrometer
characteristic hexagonal thick rod-like morphology, whereas3 the higher temperature,
hexagonal micrometer thick rod-like morphology, whereas the higher temperature, ◦
namely 240 °C led to a pure orthorhombic MoO3 phase, which was crystallizednamely
in the 240
form Cofled to
a purenanofibers.
orthorhombic MoO3 phase, of
The transformation which was crystallized
the hexagonal in the form
to orthorhombic phaseof nanofibers. The transformation
could be observed using 210
of the°C, and 3 htosynthesis
hexagonal parameters,
orthorhombic phase where
could beboth polymorphs
observed 210 ◦ C,
using were present
and 3with both types
h synthesis of
parameters,
wheremorphologies.
both polymorphsHowever,
werenot only the
present reaction
with both temperature but also the duration
types of morphologies. However, played
not an important
only the reaction
role in this
temperature butphase
alsotransformation, as it took
the duration played anplace completely
important roleonly when
in this a long
phase enough reaction as
transformation, time
it took
(6 h) was applied.
place completely only when a long enough reaction time (6 h) was applied.
3.2. Role of Additives on the Formation of MoO3
3.2. Role of Additives on the Formation of MoO3
When the CTAB additive was used, samples MoO3-7 and also MoO3-8 were identified as pure
When the CTAB additive was used, samples MoO3 -7 and
crystalline o-MoO3, similarly to those reactions, where
also MoO3 -8 were
no additive was
identified as pure
used (Figure 3a,b).
crystalline o-MoO
Experiments with 3 , similarly
the addition of CrCl3, however, resulted in a pure, metastable m-MoOExperiments
to those reactions, where no additive was used (Figure 3a,b). 3 phase
with the
(ICDDaddition of CrClat3 ,both
01-085-2405) however,
3 and resulted in adurations,
6 h reaction pure, metastable
which ism-MoO 3 phase in
unprecedented (ICDD 01-085-2405)
the literature
Nanomaterials 2020, 10, x FOR PEER REVIEW
at both 6 h reaction durations, which is unprecedented in the literature (Figure 3c,d). 6 of 13
3 and3c,d).
(Figure

Figure 3. XRD patterns of the samples synthetized in the hydrothermal reaction of AHM and HNO3
with various
Figure 3.additives, (a) MoO
XRD patterns -7 (CTAB,
of the3samples 240 ◦ C, 3inh),
synthetized the(b) MoO3 -8 (CTAB,
hydrothermal 240
reaction
◦ C, 6 h), (c) MoO -9
of AHM and HNO3 3
◦ additives, (a) MoO 3 -7 (CTAB, ◦
(CrCl3 , 240 C, 3 h), (d) MoO3 -10 (CrCl3 , 240 C, 6 h).
with various 240 °C, 3 h), (b) MoO 3 -8 (CTAB, 240 °C, 6 h), (c) MoO3-9
(CrCl3, 240 °C, 3 h), (d) MoO3-10 (CrCl3, 240 °C, 6 h).

In the case of CTAB additive, the uniform morphology typical of o-MoO3 formed here as well,
containing fibers with a diameter of 200–500 nm and a length of 10–30 μm, which were slightly
fragmented in the case of 6 h reaction time (Figure 4, MoO3-7-8).
 Figure 3. XRD patterns of the samples synthetized in the hydrothermal reaction of AHM and HNO3
with various
Nanomaterials additives,
2020, 10, 891 (a) MoO3-7 (CTAB, 240 °C, 3 h), (b) MoO3-8 (CTAB, 240 °C, 6 h), (c) MoO3-96 of 12
(CrCl3, 240 °C, 3 h), (d) MoO3-10 (CrCl3, 240 °C, 6 h).

In
In the
the case
case of
of CTAB
CTAB additive,
additive, the
the uniform
uniform morphology
morphology typical
typical of
of o-MoO formed here
o-MoO33 formed here as
as well,
well,
containing fibers with a diameter of 200–500 nm and a length of 10–30 µm, which were
containing fibers with a diameter of 200–500 nm and a length of 10–30 μm, which were slightly slightly
fragmented
fragmented in
in the
the case
case of
of 66 hh reaction
reaction time
time (Figure
(Figure 4,
4, MoO
MoO33-7-8).
-7-8).

Figure 4.4. SEM images of the samples samples synthetized

synthetized in the
the hydrothermal
hydrothermal reaction
reaction of
of AHM
AHM and and HNO
HNO33
with various additives, MoO -7: CTAB, ◦
240 °C, 3 h, MoO -8: CTAB, ◦
240 °C, 6 h, MoO
with various additives, MoO3 -7: CTAB, 240 C, 3 h, MoO3 -8: CTAB, 240 C, 6 h, MoO3 -9: CrCl3 , 240
3 3 3 -9: CrCl ◦ C,
3, 240

3°C,
h, 3MoO
h, MoO ◦
3 -10:3-10:
CrClCrCl 3, 240
3 , 240 C,°C,
6. 6.

The new
newmetastable
metastablem-MoOm-MoO 3 was crystallized
3 was in the
crystallized in form of nanosheets,
the form in contrast
of nanosheets, with the
in contrast former,
with the
longitudinal shapes shapes
former, longitudinal (columns, rods) of
(columns, the of
rods) other phases.
the other The The
phases. sheets hadhad
sheets an average
an average thickness of
thickness
100–250 nm when 3 h reaction time was applied and it increased to 100–500 nm
of 100–250 nm when 3 h reaction time was applied and it increased to 100–500 nm at 6 h duration, at 6 h duration, due to
the
duelonger reaction
to the longer time which
reaction favored
time which crystalcrystal
favored growth. The sheets
growth. were 10–20
The sheets µm long
were 10–20 μminlong
bothincases
both
and
caseswere
and arranged almostalmost
were arranged parallel to eachtoother
parallel each (Figure 4, MoO
other (Figure -9-10).3-9-10).
4,3 MoO
Examining the role of the additives, it was concluded that the CTAB additive did not influence
the formation of crystalline phases during the reaction, as it it also
also led
led toto pure
pure o-MoO
o-MoO33. On the other
hand, CTAB affected the morphology
CTAB affected the morphology resulting in a significant reduction in the diameter of of the
the fibers.
fibers.
Without the additive
additive thethe fiber
fiberdiameter
diameterofofo-MoO
o-MoO 33 was250–800
was 250–800 nm nmand and 500–1000
500–1000 nm,
nm, depending
depending on
on the duration (3 h and 6 h, respectively), but with CTAB it became much thinner, 100–250 nm and
100–500 nm in the 3 and the 6 h experiments, respectively. In contrast, the addition of CrCl3 additive
resulted in the formation of the metastable m-MoO3 , which has not been prepared by hydrothermal
synthesis previously yet. Its role in directing crystal growth also became obvious as it led to nanosheet
morphology, presumably due to its favored adherence to certain crystal planes resulting in inhibition
of crystal growth in specified directions.

3.3. Further Investigation of the Different MoO3 Phases

For a more detailed examination of hexagonal (MoO3 -1), o- (MoO3 -8), and m-MoO3 (MoO3 -10)
phases, various methods were used.
Results of the specific surface area measurement demonstrated significant differences among the
phases, which can be explained by their completely different morphologies (Table 2 SBET). The smallest
(0.21 m2 /g) specific surface area belonged to the hexagonal MoO3 phase, which was crystallized in the
form of the most robust hexagonal rods with a diameter and length of several µm. The orthorhombic
phase had the largest (9.7 m2 /g) surface area, which is attributed to its nanofibrous morphology,
whereas the size of monoclinic MoO3 nanosheets surface was 2.9 m2 /g.
 3.3. Further Investigation of the Different MoO3 Phases
For a more detailed examination of hexagonal (MoO3-1), o- (MoO3-8), and m-MoO3 (MoO3-10)
phases, various methods were used.
Results of the specific surface area measurement demonstrated significant differences among
Nanomaterials 2020, 10,which
the phases, 891 can be explained by their completely different morphologies (Table 2 SBET). The7 of 12
smallest (0.21 m /g) specific surface area belonged to the hexagonal MoO3 phase, which was
2

crystallized in the form of the most robust hexagonal rods with a diameter and length of several◦ μm.
Table 2. The specific surface area (SBET) and EDX 2results of the different MoO3 phases, MoO3 -1: 90 C,
The orthorhombic phase had the largest (9.7 m /g) surface area, which is attributed to its nanofibrous
3 h, MoO3 -8: CTAB, 240 ◦ C, 6 h, MoO3 -11: CrCl3 , 240 ◦ C, 6 h.
morphology, whereas the size of monoclinic MoO3 nanosheets surface was 2.9 m2/g.
EDX (Atom %)
Table 2.Sample
The specific surface areaSBET
(SBET)(m2 /g)
and EDX results of the different MoO3 phases, MoO3-1: 90
Mo
°C, 3 h, MoO3-8: CTAB, 240 °C, 6 h, MoO3-11: CrCl3, 240 °C, (Average)
6 h. O (Average)
MoO3 -1, hexagonal 0.21 24.3
EDX (atom %) 75.7
Sample
MoO3 -8, orthorhombic SBET (m2/g)
9.7 24.8 75.2
Mo (Average) O (Average)
MoO3 -10, monoclinic 2.9 25.7 74.3
MoO3-1, hexagonal 0.21 24.3 75.7
MoO3-8, orthorhombic 9.7 24.8 75.2
Studying the elemental composition
MoO3-10, monoclinicof the phases
2.9 by EDX,25.7
it was found that
74.3 the ratio of the main
elements (Mo, O) was close to the stoichiometric Mo:O = 1:3 ratio, and there were no other elements
referring to Studying the elemental
contaminations in thecomposition
samples. of the phases by EDX, it was found that the ratio of the main
elements (Mo, O) was close to
In the FT-IR spectra, the characteristic the stoichiometric Mo:O = 1:3(Mo-O)
metal-oxygen ratio, and there werein
vibrations nothe
other elements
range below
referring
−1 to contaminations in the samples.
1000 cm can be observed, by the help of which the phases can be distinguished (Figure 5A). Since the
In the FT-IR spectra, the characteristic metal-oxygen (Mo-O) vibrations in the range below 1000
orthorhombic and monoclinic crystal structures are very similar, their spectrum is hardly different,
cm−1 can be observed, by the help of which the phases can be distinguished (Figure 5A). Since the
unlike orthorhombic
the hexagonal andphase, where
monoclinic the structures
crystal differenceare is very
clearly visible.
similar, The intensive
their spectrum is hardlypeak around
different,
1000–900 cm −1 refers to the Mo=O band, while the other one at 550–600 cm−1 belongs to the Mo-O
unlike the hexagonal phase, where the difference is clearly visible. The intensive peak around 1000–
valence900vibration.
cm−1 refersIntothe
thecase
Mo=O ofband,
o-MoO 3 , another
while the otherless
oneintensive
at 550–600peak appearstoat
cm−1 belongs the830 cm−1
Mo-O , which
valence
is attributed to the
vibration. Mo-O-Mo
In the case of o-MoOdeformation vibration
3, another less intensive andpeakit appears
is not present
at 830 cmin ,the
−1 whichspectrum of the
is attributed
to thephase.
monoclinic Mo-O-Mo In deformation
contrast, invibration and it isof
the spectrum notthepresent
h-MoO in the
3 spectrum
phase, a of
band the monoclinic
can be phase.
observed at
In contrast,
−1 in the spectrum of the h-MoO 3 phase, a band can be observed at 700–750 cm−1 referring to
700–750 cm referring to the Mo-O vibration, which does not appear in the case of the other two
phases.the Mo-O vibration,
In addition, peaks which
around does
1400 notand
appear
3200incm the
−1 ,case of the other
moreover twoand
at 1600 phases.
3400Incm addition,
−1 belong peaks
to the
around 1400 and 3200 cm −1, moreover at 1600 and 3400 cm−1 belong to the N-H vibrations of the NH4+
N-H vibrations of the NH4 + group and to the O-H vibrations of O-H groups and water molecules,
group and to the O-H vibrations of O-H groups and water molecules, respectively. These bands are
respectively. These bands are not detectable in the case of orthorhombic and monoclinic MoO3 phases.
not detectable in the case of orthorhombic and monoclinic MoO3 phases. This phenomenon can be
This phenomenon
explained bycan the be
factexplained
that hexagonalby the fact that
channels hexagonal
usually channels
store small ions, usually
e.g., NHstore small ions, e.g.,
4+ or molecules e.g.,
NH4 + orH2molecules e.g., Hthe
O which stabilize 2 Ostructure,
which stabilize theh-WO
similar to structure, similar to h-WO3 [2,11,15,34,35].
3.[2,11,15,34,35].

Nanomaterials 2020, 10, x FOR PEER REVIEW 8 of 13

5. FT-IR
Figure Figure (A), Raman
5. FT-IR (A), Raman (B), (B),
andandUV–Vis
UV–Vis (C)(C) spectra
spectraofofdifferent
different MoO phases,(a)(a)MoO
MoO33 phases, MoO 3 -10,
3-10,

monoclinic phase phase

(CrCl3(CrCl ◦
, 2403, 240
C, 6°C,
h),6(b) ◦
monoclinic h), MoO 3 -8,3-8,
(b) MoO orthorhombic
orthorhombicphase
phase(CTAB,
(CTAB, 240 C, 66 h),
240 °C, h),(c)
(c)MoO
MoO 3-3 -1,

hexagonal phase (90

1, hexagonal ◦ C, 3
phase h).°C, 3 h).
(90

In the In
Raman spectra,
the Raman the distinctive
spectra, bands
the distinctive of of
bands o-MoO
o-MoO3 3at
at990,
990, 820, and 680
820, and 680cmcm−1−1 belong
belong to the
to the
stretching mode of Mo=O 1, Mo-O 3 -Mo, and the Mo-O 2-Mo (Figure 5B). The peaks appearing
stretching mode of Mo=O1 , Mo-O3 -Mo, and the Mo-O2 -Mo (Figure 5B). The peaks appearing between between
400 and 170 cm−1 refer to the different deformation vibrations of O=Mo=O and O-Mo-O, while those
below 170 cm−1 are derived from the translation of rigid MoO4 chain. The monoclinic phase has a
similar Raman spectrum, but at 500 cm−1 there is a band of the Mo-O valence vibration that is absent
in the spectrum of the orthorhombic MoO3 and there are evident differences between o- and m-MoO3
in the ratio of the peaks, as well, mostly in the range of deformation vibrations. In the case of h-MoO3,
the band at 1000 cm−1 and the triple peak located at 910–900–880 cm−1 are ascribed to the Mo=O
Nanomaterials 2020, 10, 891 8 of 12

400 and 170 cm−1 refer to the different deformation vibrations of O=Mo=O and O-Mo-O, while those
below 170 cm−1 are derived from the translation of rigid MoO4 chain. The monoclinic phase has
a similar Raman spectrum, but at 500 cm−1 there is a band of the Mo-O valence vibration that is
absent in the spectrum of the orthorhombic MoO3 and there are evident differences between o- and
m-MoO3 in the ratio of the peaks, as well, mostly in the range of deformation vibrations. In the case
of h-MoO3 , the band at 1000 cm−1 and the triple peak located at 910–900–880 cm−1 are ascribed to
the Mo=O valence vibrations, whereas the bands around 700, 500, 390, and 320 cm−1 refer to the
O-Mo-O vibrations. The peaks below 300 cm−1 are attributed to the modes of the MoO4 tetrahedra
chains [36–39].
The absorption properties of the phases were investigated by diffuse reflectance UV–Vis
spectroscopy. In each spectrum, a distinct absorption edge can be observed, which is characteristic of
semiconductors (Figure 5C). Every phase absorbs not only in the UV range, but also in the visible part
of the spectrum. The hexagonal phase, due to its pale yellow color, absorbs only below 500 nm, while
the blue colored orthorhombic phase has absorption also above 550 nm, and so does monoclinic MoO3 .
Based on the spectra, the band gaps were determined, which were 3.07 eV for h-MoO3 , 3.33 eV for
o-MoO3 , and 3.02 eV for m-MoO3 .

3.4. Gas Sensing

3.4.1. Checking Crystalline Phases and Morphology at 500 ◦ C

The gas sensing properties were tested between room temperature up to 500 ◦ C. However, at
lower temperatures the gas sensing signals were so small that they could not be evaluated properly.
Therefore, the responses to various H2 gas concentrations were only recorded at 500 ◦ C. Accordingly,
the present study serves only as a short test about the gas sensing of hydrothermally prepared m-MO3 ,
but later a more detailed study is needed with lower sensing temperatures and various test gases.
Due to the relatively high operating temperature, before the gas sensing investigations, it was
needed to check the possible phase and morphology transformations occurring at 500 ◦ C, at the
temperature of the gas sensing tests. Hence, all the MoO3 polymorphs had a 1 h heat treatment at
◦ C, and then they were studied by XRD and SEM (Figure 6).
500Nanomaterials 2020, 10, x FOR PEER REVIEW 9 of 13

Figure 6. XRD patterns (A) and SEM images of different MoO3 phases after the 500 °C heat treatment.,
Figure 6. XRD patterns (A) and SEM images of different MoO3 phases
(a) MoO3-10, monoclinic phase (CrCl3, 240 °C, 6 h), (b) MoO3-8, orthorhombic
after the 500 ◦ C heat treatment.,
phase (CTAB, 240 °C, 6
(a)h),MoO 3 -10,
(c) MoO monoclinic phase (CrCl3 , 240 C, 6 h), (b) MoO3 -8, orthorhombic phase (CTAB, 240 ◦ C,
3-1, hexagonal phase (90 °C, 3 h).
◦

6 h), (c) MoO3 -1, hexagonal phase (90 ◦ C, 3 h).

3.4.2. Gas Sensing Tests
During the tests the samples gave an n-type response, namely, their electrical resistance was
reduced when exposed to hydrogen, which is typical for an n-type semiconductor reacting to a
reducing gas [40]. The change in the logarithm of their electrical resistance as a function of time is
presented in (Figure 7A–C). The sensitivity (S) of the sensors can be calculated using the following
|∆ |
formula [41]: 𝑆 = , where ∆R is the change in electrical resistance due to the presence of the gas,
Nanomaterials 2020, 10, 891 9 of 12

Based on SEM and XRD results, we concluded that the heat treatment did not change the phase
and morphology of o- and m-MoO3 . However, the initially h-MoO3 phase transformed into o-MoO3 ,
and the morphology changed, as well. The heated h-MoO3 (now o-MoO3 ) samples consisted of no
hexagonal rods as before, but 10–20 nm wide, 200–300 nm long side-adhered plates, and irregular
particles in various sizes (10–500 nm, Figure 6).

3.4.2. Gas Sensing Tests

During the tests the samples gave an n-type response, namely, their electrical resistance was
reduced when exposed to hydrogen, which is typical for an n-type semiconductor reacting to a
reducing gas [40]. The change in the logarithm of their electrical resistance as a function of time is
presented in (Figure 7A–C). The sensitivity (S) of the sensors can be calculated using the following
formula [41]: S = R|∆R| , where ∆R is the change in electrical resistance due to the presence of the gas,
base
while Rbase is the baseline electrical resistance of the material. As the baseline did not slip significantly,
we selected the measured electrical resistance before the introduction of the 25,000 ppm H2 gas as Rbase .
It can be observed that the sensitivity does not increase linearly with the increasing H2 concentration,
and this might be related to the saturation of the gas sensing active sites (Figure 7D). Based on the gas
sensing results, m- (β-) MoO3 is more sensitive to the H2 gas than o- (α-) MoO3 which has, however,
a larger specific surface area. Probably the density of surface active site is different in their case, which
can be explained by, e.g., different amounts and forms of pre-adsorbed oxygen (O2− , O− or O2 − ) or
the difference in surface OH groups similar to m- and h-WO3 [40,42]. The annealed h-MO3 , which
transformed into o-MoO3 at 500 ◦ C has a similar sensitivity to the monoclinic polymorph. Probably
the hexagonal-orthorhombic transformation caused an increase in the number of active sites or in the
surface area, which
Nanomaterials 2020, 10,might explain
x FOR PEER this.
REVIEW 10 of 13

1.0
D)
0.8
Sensitivity (a.u.)

0.6

• β-MoO3
0.4
• h-MoO3
• α-MoO3
0.2
0 5000 10000 15000 20000 25000
H2 concentration (ppm)

Figure 7. Results
Figure 7. Resultsof of
thethe
gas sensing
gas sensingtest
testofofthe
thedifferent
differentMoO
MoO33 phases. (A) MoO
phases. (A) MoO3-10,
3 -10,monoclinic
monoclinicphase
phase
(CrCl ◦ ◦
3 , 240
(CrCl C, 6 h); (B) MoO -8,
3, 240 °C, 6 h); (B) MoO33
-8,orthorhombic
orthorhombic phase
phase (CTAB,
(CTAB, 2406 h);
240 °C, C, (C)
6 h); (C)3-1,
MoO MoO 3 -1, hexagonal
hexagonal phase
phase (90 ◦ C, 3 h); (D) sensitivity of the MoO polymorphs.
(90 °C, 3 h); (D) sensitivity of the MoO3 polymorphs. 3

Table 3. Response and return times of sensors using 25,000 ppm H2.

Sample Response Time (min) Recovery Time (min)

MoO3-10, monoclinic 1.2 22.5
MoO3-8, orthorhombic 1.2 10.1
Nanomaterials 2020, 10, 891 10 of 12

The response time was defined as the time at which the electrical resistance reaches 90% of the
maximum signal given to a certain gas concentration and the recovery time was defined as the time
needed to return to 10% of the maximum signal after finishing the gas pulse. These values are given
for each sample using 25,000 ppm H2 (Table 3). Based on the data, the response time of all samples
is low, approx. 1 min. The samples with a similar sensitivity (monoclinic and transformed hexagonal)
also have a similar recovery time, approx. 20 min. The recovery time was lower for the fiber-like
o-MoO3 sample. This might be explained by its lower number of gas sensing active sites, which also
explained the lower sensitivity of this sample.

Table 3. Response and return times of sensors using 25,000 ppm H2 .

Sample Response Time (min) Recovery Time (min)

MoO3 -10, monoclinic 1.2 22.5
MoO3 -8, orthorhombic 1.2 10.1
MoO3 -1, hexagonal 1.2 20.3

4. Conclusions
In this study, we investigated the effect of various parameters on the hydrothermal preparation
of MoO3 , for the first time also at 240 ◦ C, focusing on the changes in the crystalline phases and
morphology of the products. We used different temperatures (90/210/240 ◦ C) and durations (3/6 h) to
investigate their role in our reaction system. At 240 ◦ C, we also tested the effect of CTAB and CrCl3
additives, respectively. As a result, h-MoO3 formed at 90 ◦ C independently on the duration and
crystallized in the form of hexagonal rods. At 210 ◦ C with 3 h reaction time, the product was a mixture
of h- and o-MoO3 , while with 6 h it was pure o-MoO3 , alike at 240 ◦ C, with nanofibrous morphology.
With the use of the CTAB additive, we obtained pure o-MoO3 in the form of nanofibers, but with a
radically reduced diameter due to the presence of the additive. However, when we applied CrCl3 ,
it resulted in the metastable m-MoO3 phase at both reaction durations with nanosheet morphology.
The gas sensing properties of the MoO3 samples against H2 were also tested. The m-MoO3 was found
to be more sensitive than the o-MoO3 .

Author Contributions: Conceptualization, T.N.-K., I.M.S., and G.P.; methodology, T.N.-K. and I.M.S.; investigation,
T.N.-K., L.S., I.E.L., K.L., and P.P.; writing—original draft preparation, T.N.-K.; writing—review and editing,
K.L., P.P., I.M.S., and G.P.; supervision, I.M.S. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by NRDI grant numbers K 124212, TNN_16 123631. The work performed
within project no. VEKOP-2.3.2-16-2017-00013 was supported by the European Union and the State of Hungary,
co-financed by the European Regional Development Fund. The research reported in this paper was supported by
the Higher Education Excellence Program of the Ministry of Human Capacities in the frame of Nanotechnology
and Materials Science research area of Budapest University of Technology (BME FIKP-NAT). The APC was funded
by the Budapest University of Technology and Economics.
Acknowledgments: The authors thank T. Igricz (Budapest University of Technology and Economics, Department
of Organic Chemistry and Technology) for help in the Raman measurements.
Conflicts of Interest: The authors declare no conflict of interest.

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