nanomaterials
Article
Simple Synthesis of Molybdenum Carbides from Molybdenum
Blue Nanoparticles
Natalia Gavrilova 1, *, Maria Myachina 1 , Victor Nazarov 1






Citation: Gavrilova, N.; Myachina,
M.; Nazarov, V.; Skudin, V. Simple
Synthesis of Molybdenum Carbides
from Molybdenum Blue
Nanoparticles. Nanomaterials 2021, 11,
873. https://doi.org/10.3390/
nano11040873
Academic Editor:
Andres Castellanos-Gomez
Received: 8 March 2021
Accepted: 29 March 2021
Published: 30 March 2021
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Copyright: © 2021 by the authors.
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conditions of the Creative Commons
Attribution (CC BY) license (https://
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4.0/).
Nanomaterials 2021, 11, 873. https://doi.org/10.3390/nano11040873
and Valery Skudin 2
1 Department of Colloid Chemistry, Faculty of Natural Sciences, D. Mendeleev University of Chemical
Technology of Russia, Miusskaya sq., 9, 125047 Moscow, Russia; mmyachina@muctr.ru (M.M.);
nazarov@muctr.ru (V.N.)
2 Department of Chemical Technology of Carbon Materials, Faculty of Petroleum Chemistry and Polymers,
D. Mendeleev University of Chemical Technology of Russia, Miusskaya sq., 9, 125047 Moscow, Russia;
skudin@muctr.ru
* Correspondence: ngavrilova@muctr.ru
Abstract: In recent years, much attention has been paid to the development of a new flexible and
variable method for molybdenum carbide (Mo2 C) synthesis. This work reports the applicability of
nano-size clusters of molybdenum blue to molybdenum carbide production by thermal treatment
of molybdenum blue xerogels in an inert atmosphere. The method developed made it possible to
vary the type (glucose, hydroquinone) and content of the organic reducing agent (molar ratio R/Mo).
The effect of these parameters on the phase composition and specific surface area of molybdenum
carbides and their catalytic activity was investigated. TEM, UV–VIS spectroscopy, DTA, SEM, XRD,
and nitrogen adsorption were performed to characterize nanoparticles and molybdenum carbide.
The results showed that, depending on the synthesis conditions, variants of molybdenum carbide
can be formed: α-Mo2 C, η-MoC, or γ-MoC. The synthesized samples had a high specific surface
area (7.1–203.0 m2 /g) and meso- and microporosity. The samples also showed high catalytic activity
during the dry reforming of methane. The proposed synthesis method is simple and variable and
can be successfully used to obtain both Mo2 C-based powder and supports catalysts.
Keywords: molybdenum carbide; molybdenum blue; nanoclusters; dispersion; sol-gel method
1. Introduction
In recent years, the development of catalysts based on transition metal carbides has
become increasingly important in chemical technology. Transition metal carbides show
high hardness, thermal stability, and catalytic properties similar to Pt group metals [1,2].
One such promising catalyst is molybdenum carbide, Mo2 C. Molybdenum show high
selectivity and activity in many reactions, such as isomerization, ammonia synthesis, water–
gas shift reaction, hydrocarbon reforming, and H2 production [3–9]. Molybdenum carbides
also demonstrate resistance to poison [10–12], so they are considered an alternative to
platinum-group catalysts.
The most widely used method of synthesizing molybdenum carbides is the temperature-
programmed reaction (TPRe), which involves gas–solid reactions. Molybdenum oxides
are used as a molybdenum precursor and a mixture of hydrocarbon gases (Cn H2n+2 /H2 )
as a carbon source [13–20]. Studies on molybdenum carbide synthesis via the TPRe have
specified various conditions: the rate of temperature change, the final temperature of the
process, the carbon source, and the H2 /Cn H2n+2 ratio. The choice of activating mixtures
affects the specific surface area, morphology, and particle size of the resulting carbide, as
well as its catalytic activity [19,20]. This method usually forms β-Mo2 C. Preparing other
phases, such as monocarbides (MoC), however, requires a complex synthesis procedure
involving preliminary nitridation of molybdenum oxides, followed by the carbidation of
https://www.mdpi.com/journal/nanomaterials
Nanomaterials 2021, 11, 873 2 of 14

molybdenum nitride, pretreatment with hydrogen, or treatment of molybdenum oxides at

high pressure [21,22].
Despite its advantages, the TPRe has a few limitations. First, it involves the use of
explosive mixtures (hydrocarbon and hydrogen), which requires certain safety measures.
Second, hydrocarbon interaction inevitably forms carbon, which is deposited as a polymer
film on the catalyst surface, blocking active sites [23]. In addition, the process of obtaining
supported catalysts is complex. At the first stage, it is necessary to use molybdenum salt
solutions for the impregnation of supports, followed by calcination, and then the MoO3
supported catalysts are carburized using the gas mixtures described above [24,25].
Among the various methods for molybdenum carbide synthesis, soft chemistry, which
provides an opportunity to obtain molybdenum carbides at relatively low temperatures
or under mild conditions, is especially important. In most cases, liquid-phase systems
containing molybdenum salts are a molybdenum source and organic compounds are a
carbon source. The resulting precipitate or gel is subsequently sintered in an inert atmo-
sphere. For example, in [26–28], molybdenum carbide was produced using ammonium
heptamolybdate or pentachloride and glucose, sucrose, alanine, or urea. In [26], the authors
emphasized that a novel method (sol-gel-like synthesis) of transition metal carbide produc-
tion exists and is in high demand. The observed sol-gel transition opens up the possibility of
obtaining various Mo2 C-based materials such as fibers, coatings, and supported catalysts.
Molybdenum polyoxometalate structures, represented by molybdenum oxide clusters
of various shapes and sizes, are of great interest in this area of research. Molybdenum
blue nanoparticles are dispersions of molybdenum oxide clusters in which molybdenum is
present in +5 and +6 oxidation states. These compounds can be obtained by the reduction
of molybdates at pH ≤ 3 [29–31]. Organic compounds can be used as reducing agents,
which will act as a carbon source in molybdenum carbide synthesis.
For many years, molybdenum blue nanoparticles were considered interesting ex-
clusively in inorganic chemistry. However, they can also be used in the preparation of
different catalysts due to the peculiarities of their synthesis and structure. Their small size,
monodispersity, and the presence of partially reduced molybdenum make them promising
precursors for molybdenum carbide synthesis.
Oxide clusters in the molybdenum blues are so large that they can be considered
as hydrosols. This makes them convenient for the sol-gel technology using all of the
advantages of the sol-gel method: the possibility of deposition on porous and nonporous
supports, morphology control, and the porosity and thickness of the catalytic layer.
A molybdenum blue dispersion synthesized with ascorbic acid was successfully
used to prepare Mo2 C [32]. The molar ratio (R/Mo) is the main parameter that affects
the morphology, pore structure, and phase composition of molybdenum carbide. At a
low R/Mo molar ratio, monophase mesoporous β-Mo2 C is formed, while increasing the
reducing agent content leads to the formation of a second phase, η-MoC.
Stable molybdenum blue dispersions from the viewpoint of aggregative and chemical
stability can also be obtained by using other reducing agents such as glucose [33] and
hydroquinone [34], and it would be interesting to study the possibility of using these
dispersions for molybdenum carbide synthesis.
In this study we synthesized molybdenum carbides using molybdenum blue and
organic reducing agents (glucose and hydroquinone) and investigated the effect of the type
and content of the reducing agent on the morphology, phase composition, and surface area
of the synthesized molybdenum carbides. The results open up the possibility of a simple
route of sol-gel synthesis for the molybdenum carbides and catalysts based on them.

2. Materials and Methods

2.1. Materials
Ammonium heptamolybdate (NH4 )6 Mo7 O24 ·4H2 O, glucose (C6 H12 O6 ), hydroquinone
(C6 H6 O2 ), and hydrochloric acid (HCl) were used as precursors for molybdenum blue dis-
persion synthesis. All chemicals used were laboratory grades (CT Lantan, Moscow, Russia).
Nanomaterials 2021, 11, 873 3 of 14

2.2. Molybdenum Blue Synthesis

A strictly defined amount of an organic reducing agent was added to ammonium
heptamolybdate solution (0.07 M) with vigorous stirring, and then hydrochloric acid was
added until the pH reached 2.0. The reaction was carried out at room temperature.
The synthesis conditions were as follows: molar ratio R/Mo = 4.0–7.0, molar ratio
of hydrochloric acid and molybdenum H/Mo = 0.5 for glucose and R/Mo = 4.0–9.0, and
molar ratio H/Mo = 3.0 for hydroquinone.
To synthesize 50 mL of molybdenum blue dispersion using glucose, 10.6 mL of
ammonium heptamolybdate solution (0.047 M), 0.3 mL of hydrochloric acid (2.46 M),
and 2.52–4.41 g of glucose powder (R/Mo = 4.0–7.0) were used. To synthesize 50 mL of
molybdenum blue dispersion using hydroquinone, 10.6 mL of ammonium heptamolybdate
solution (0.047 M), 4.2 mL of hydrochloric acid (2.46 M), and 1.54–3.47 g of hydroquinone
powder (R/Mo = 4.0–9.0) were used.
These conditions were set based on previous experiments to form stable (aggregative
and chemical) molybdenum blue dispersions [33,34].

2.3. Molybdenum Blue Dispersions Characterization

TEM was performed using a LEO 912 AB Omega microscope (Carl Zeiss, Jena, Germany)
to determine the particle size distribution. XPS spectra were recorded on an ESCA+X-ray
photoelectron spectrometer (OMICRON Nanotechnology, Taunusstein, Germany). UV–VIS
spectra were recorded using a Leki SS2110 UV scanning spectrophotometer (MEDIORA
OY, Helsinki, Finland).

2.4. Molybdenum Carbide Synthesis

Xerogels were obtained by drying molybdenum blue dispersions at room temperature.
Molybdenum carbides were prepared by thermal decomposition of the xerogels; thermal
treatment was carried out in a N2 atmosphere at 900 ◦ C.
For further experiments, the following samples were synthesized: G-4, G-5, G-6, and
G-7 (reducing agent, glucose; number, molar ratio R/Mo) and H-4, H-5, H-6, H-7, H-8, and
H-9 (reducing agent, hydroquinone; number, molar ratio R/Mo).

2.5. Molybdenum Carbide Characterization

Thermal analysis (DTA) of xerogels was performed using an SDT Q600 thermal
analyzer (TA Instruments, New Castle, DE, USA) in inert atmosphere. XRD patterns were
recorded using a Rigaku D/MAX 2500 diffractometer (Rigaku Corporation, Tokyo, Japan)
with CuKα radiation at a scanning step of 0.02 and a scanning range (2θ) of 20◦ –90◦ . The
specific surface area (Sa ) of the samples was determined using Gemini VII (Micromeritics,
Norcross, GA, USA) by applying the standard Brunauer–Emmett–Teller (BET) method.
The total specific pore volume (ΣV) was determined at a maximum relative pressure of
0.995, and the pore size distribution was calculated using BJH (mesopores) and Horvath–
Kawazoe (micropores) methods. The volume of micropores was determined using the
Dubinin–Radushkevich equation and a t-plot.

2.6. Catalytic Tests

The catalytic activity of the synthesized molybdenum carbide samples (G-7, H-4) in
dry reforming of methane was evaluated using a fixed-bed reactor at atmospheric pressure
and temperature 800 ◦ C–870 ◦ C. The feed gas mixture comprised an equimolar mixture of
CH4 and CO2 . Gas compositions were monitored using a Crystall 5000 gas chromatograph
(CJSC SKB Chromatec, Yoshkar-Ola, Russia) equipped with two thermal conductivity
detectors and chromatographic columns (HayeSep R 80/100, NaX 60/80).
The parameters of catalytic activity (the rate constant k900 and specific rate constant
900
ks ) were calculated according to the work [32].
 2.6. Catalytic Tests
The catalytic activity of the synthesized molybdenum carbide samples (G-7, H-4) in
dry reforming of methane was evaluated using a fixed-bed reactor at atmospheric pres-
Nanomaterials 2021, 11, 873 sure and temperature 800 °C–870 °C. The feed gas mixture comprised an equimolar mix- 4 of 14
ture of CH4 and CO2. Gas compositions were monitored using a Crystall 5000 gas chro-
matograph (CJSC SKB Chromatec, Yoshkar-Ola, Russia) equipped with two thermal con-
ductivity detectors and chromatographic columns (HayeSep R 80/100, NaX 60/80).
The parameters of catalytic activity (the rate constant k900 and specific rate constant
3. Results
ks900) were calculated according to the work [32].
3.1. Molybdenum Blue Dispersion Characterization
3. Results Molybdenum blue dispersions were synthesized by the reduction of ammonium
3.1. Molybdenum Blue Dispersion
heptamolybdate in an Characterization
acidic medium. Glucose and hydroquinone were used as reducing
Molybdenum
agents due tobluethe
dispersions wereof
possibility synthesized
using them by theasreduction
a carbon of ammonium
source in subsequent further
heptamolybdate in an acidic medium. Glucose and hydroquinone were used as reducing
molybdenum carbide synthesis.
agents due to the possibility of using them as a carbon source in subsequent further mo-
lybdenumFigure
carbide 1 shows TEM micrographs of synthesized molybdenum blue dispersions. The
synthesis.
dispersed phase
Figure 1 shows TEM was represented
micrographs by particles
of synthesized less than
molybdenum 5 nm in size.
blue dispersions. The The most probable
dispersed phase
particle was represented
diameter by particles
calculated less than size
from particle 5 nm measurements
in size. The most probable
was around 3 nm.
particle diameter calculated from particle size measurements was around 3 nm.

(a) (b)
Figure 1. TEM images of particles and particle size distribution of molybdenum blue dispersions
Figure 1. TEM images of particles and particle size distribution of molybdenum blue dispersions
synthesized using various reducing agents: (a) glucose and (b) hydroquinone.
synthesized using various reducing agents: (a) glucose and (b) hydroquinone.
Figure 2 shows the absorption spectra of the synthesized molybdenum blue disper-
sions. TheFigure 2 showsabsorption
two characteristic the absorption spectra
bands in the visibleof the
part of synthesized molybdenum
the spectrum (750 nm) blue disper-
and sions.
the near-IR
Theregion
two (1050 nm) indicated
characteristic not only thebands
absorption presence
inofthe
reduced molybdenum
visible part of the spectrum (750 nm)
but also the toroidal shape of particles of the dispersed phase (molybdenum oxide clus-
and the near-IR region (1050 nm) indicated not only the presence of reduced molybde-
ters) [29,35,36].
Nanomaterials 2021, 11, x FOR PEER REVIEW 5 of 16
num but also the toroidal shape of particles of the dispersed phase (molybdenum oxide
clusters) [29,35,36].

2
Absorbance

750 1050
2
1
0
400 600 800 1000 1200
λ, nm

Figure 2. Electronic absorption spectra of molybdenum blue nanoparticles synthesized using various
Figure 2. Electronic absorption spectra of molybdenum blue nanoparticles synthesized using vari-
reducing
ous reducing agents:
agents: glucose glucose
(1) and (1) and
hydroquinone (2). hydroquinone (2).

3.2. Synthesis of Molybdenum Carbides from Molybdenum Blue Dispersions

3.2. Synthesis of Molybdenum Carbides from Molybdenum Blue Dispersions
To determine the temperature required to obtain molybdenum carbides, thermo-
To determine
gravimetric analysis the
of molybdenum temperature
blue required
xerogels synthesized to obtain
using glucose molybdenum
carbides, thermogravi-
and hydro-
quinone was performed (Figure 3).
metric analysis of molybdenum blue xerogels synthesized using glucose and hydroquinone
was performed (Figure 3).
The sample weight loss occurred stepwise in several stages. The first stage occurred
at 100 ◦ C and 180 ◦ C and was associated with the removal of free and bound water. Simul-
taneously, several endothermic effects were recorded on the DTA curves. At temperatures
above 350 ◦ C, the decomposition of organic substances and ammonium chloride began. In
this region, a diffuse exothermic effect was observed, with a maximum at ~350 ◦ C.
 1
0
400 600 800 1000 1200
λ, nm

Figure 2. Electronic absorption spectra of molybdenum blue nanoparticles synthesized using vari-
ous reducing agents: glucose (1) and hydroquinone (2).
Nanomaterials 2021, 11, 873 5 of 14
3.2. Synthesis of Molybdenum Carbides from Molybdenum Blue Dispersions
To determine the temperature required to obtain molybdenum carbides, thermo-
gravimetric analysis of molybdenum blue xerogels synthesized using glucose and hydro-
quinone was performed (Figure 3).

Nanomaterials 2021, 11, x FOR PEER REVIEW 6 of 16

The sample Figure

Figure 3. TG 3.
weight andTG
loss
DTA and
occurred DTA
curves of curves
stepwise
molybdenum in of molybdenum
several
blue xerogels stages. The
synthesized blue
first
using xerogels
stage
glucose synthesized using glucose (black lines)
occurred
(black
lines)°C
at 100 °C and 180 andand
hydroquinone
was (red lines). with the removal of free and bound water. Sim-
associated
and hydroquinone (red lines).
ultaneously, several endothermic effects were recorded on the DTA curves. At tempera-
tures above 350 °C, the decomposition of organic substances and ammonium chloride ◦ be- ◦ C. These changes indicated
The last
gan. In this region, a diffuse stageeffect
exothermic of mass change
was observed, withbegan
a maximum at 680at ~350C–750
°C.
theofforming
The last stage mass change of began
carbide from
at 680 °C–750 carbon
°C. These and molybdenum
changes indicated the oxides, accompanied by a slight
forming of carbide from carbon
endothermic effect. and molybdenum oxides, accompanied by a slight endo-
thermic effect.
To analyze the changesTo analyze the product
in the solid changes in thedecomposition,
of xerogel solid product of xerogel
a series of decomposition, a series of
samples
samples were prepared, wereatprepared,
calcined calcined and
different temperatures, at different
subjected totemperatures,
X-ray phase and subjected to X-ray phase
analysis (Figureanalysis
4). (Figure 4).

- Carbon
- MoO2[32-0671]
- α−Mo2C [35-0787]

900 0С
Intentsity, a.u.

800 0С

700 0С
600 0С
500 0С
400 0С
20 30 40 50 60 70 80
2Θ, degr.

(a)

- Carbon
- MoO2[32-0671]
- α−Mo2C [35-0787]
- γ-МоС [45-1015]

Δ
Intensity, a.u.

Δ
Δ
900 0С
800 0С

700 0С

600 0С

510 0С
10 20 30 40 50 60 70 80 90
2Θ, degr.

(b)

Figure 4. XRD pattern of molybdenum blue xerogels synthesized using (a) glucose (G-4, R/Mo = 4.0)
and (b) hydroquinone (H-4, R/Mo = 4.0), calcined at different temperatures in an inert N2 atmosphere.
Nanomaterials 2021, 11, 873 6 of 14
Nanomaterials 2021, 11, x FOR PEER REVIEW 7 of 16

FigureThe4. XRDdiffractograms
pattern of molybdenumshowed two diffuse
blue xerogels synthesizedreflections for (G-4,
using (a) glucose molybdenum
R/Mo = blue xerogels
4.0) and (b) hydroquinone
synthesized (H-4, R/Mo(Figure
using glucose = 4.0), calcined
4a),atcalcined
different temperatures in an inert Nof
at temperatures 2 at-
600 ◦ C and below,
mosphere.
corresponding to amorphous carbon. Reflections of another phase (molybdenum com-
pounds) began to appear at two
temperatures above ◦ C. These reflections (26.0, 37.0, 53.1,
The diffractograms showed diffuse reflections for600
molybdenum blue xerogels
60.2) corresponded
synthesized using glucoseto monoclinic molybdenum
(Figure 4a), calcined dioxide,
at temperatures of 600MoO
°C and 2 (32-0671).
below, cor- The carbon and
responding to amorphous carbon. Reflections of another
molybdenum dioxide phases were present in the diffraction patterns up phase (molybdenum com-to temperatures of
pounds)
◦ began ◦ to appear at◦ temperatures above 600 °C. These reflections (26.0, 37.0, 53.1,
800 C–830 C. At 900 C, characteristic reflections of hexagonal
60.2) corresponded to monoclinic molybdenum dioxide, MoO2 (32-0671). The carbon and
α-Mo 2 C (35-0787) appeared.
In contrast
molybdenum to phases
dioxide the series
were of samples
present in the synthesized using
diffraction patterns up glucose, there was practically
to temperatures
no amorphous
of 800 °C–830 °C. At carbon
900 °C,in the diffractograms
characteristic reflections ofof the series
hexagonal α-Moof2C samples
(35-0787) ap- synthesized using
peared.
hydroquinone, since the excess reducing agent present in the xerogels sublimed (Figure 4b).
In contrast to the series of samples synthesized using glucose, there was practically
Therefore, the reflections of molybdenum compounds were clearly visible. At temperatures
no amorphous
◦ C–700 carbon
◦ C, in the diffractograms of the series of samples synthesized using hy-
of 500
droquinone, since the therereducing
excess was one agent phase
present ofinmolybdenum dioxide,
the xerogels sublimed (FigureMoO
4b). 2 (32-0671). An
increase ◦
Therefore,in thetemperature to 800 C led
reflections of molybdenum to the formation
compounds were clearlyof molybdenum
visible. At tempera- carbide α-Mo2 C
tures of 500 °C–700
(35-0787). °C, there obtained
For samples was one phase by ofcalcination 900 ◦ C,
molybdenumatdioxide, MoOthe2 (32-0671).
presence Anof two phases of
increase in temperature to 800 °C led to the formation of molybdenum
α-Mo2 C and γ-MoC (45-1015) was observed. Analysis of the literature2Cdata showed that carbide α-Mo
(35-0787). For samples obtained by calcination at 900 °C, the presence of two phases of α-
the solid–liquid phase method has not yet succeeded in obtaining γ-MoC or its mixture
Mo2C and γ-MoC (45-1015) was observed. Analysis of the literature data showed that the
with α-Mo2phase
solid–liquid C [9].method has not yet succeeded in obtaining γ-MoC or its mixture with
α-MoTo determine the effect of the reducing agent content on the phase composition of
2C [9].

To determine
molybdenum the effect
carbide of the reducing
obtained from agent content on the
molybdenum bluephase compositionaofseries of samples
dispersions,
molybdenum carbide obtained from molybdenum blue dispersions, a series of samples
with the molar ratio R/Mo = 4–9 was prepared. The calcination temperature of the samples
with the molar
◦ ratio R/Mo = 4–9 was prepared. The calcination temperature of the samples
was
was 900
900 °C.C. The
The results
results are shown
are shown in Figure in5.Figure 5.

- C
- MoO2[32-0671]
- α−Mo2C [35-0787]
Δ - η-МоС [08-0384]
Δ Δ
Intensity, a.u.

[R]/[Mo] = 9
Δ ΔΔ

[R]/[Mo] = 7

[R]/[Mo] = 5

[R]/[Mo] = 4

10
Nanomaterials 2021, 11, x FOR PEER REVIEW 20 30 40 50 60 70 80 8 of 16
2Θ, degr.
(a)
- γ-МоС [45-1015]
Intensity, a.u.

[R]/[Mo] = 9

[R]/[Mo] = 8

[R]/[Mo] = 7

[R]/[Mo] = 6

[R]/[Mo] = 5

[R]/[Mo] = 4

20 30 40 50 60 70 80 90
2Θ, degr.
(b)
Figure 5. XRD pattern of molybdenum blue xerogels synthesized using (a) glucose and (b) hydro-
Figure 5. XRD pattern of molybdenum blue xerogels synthesized using (a) glucose and (b) hydro-
quinone with different R/Mo molar ratios calcined at 900 °C in an inert N2 atmosphere.
quinone with different R/Mo molar ratios calcined at 900 ◦ C in an inert N2 atmosphere.
Samples with a low reducing agent content (glucose, R/Mo = 4–5) were characterized
by the presence of one phase of molybdenum carbide, β-Mo2C (35-0787). The sample with
R/Mo = 5 was characterized by the maximum intensity of reflections of the β-Mo2C phase
and the lowest intensity of reflections of free carbon (see Figure 5a). This indicated the
completeness of the carbide formation from its precursors. An increase in the reducing
agent content led to the appearance of η-MoC and an increase in free amorphous carbon.
The results are in good agreement with the phase diagram, according to which η-MoC is
formed in the presence of the excess carbon [37].
 20 30 40 50 60 70 80 90
2Θ, degr.
(b)
Nanomaterials 2021, 11, 873 7 of 14
Figure 5. XRD pattern of molybdenum blue xerogels synthesized using (a) glucose and (b) hydro-
quinone with different R/Mo molar ratios calcined at 900 °C in an inert N2 atmosphere.

Samples with a low

Samples withreducing agent content
a low reducing (glucose,
agent content R/Mo =R/Mo
(glucose, 4–5) were characterized
= 4–5) were characterized
by the presence of one phase of molybdenum carbide, β-Mo 2C (35-0787). The sample with
by the presence of one phase of molybdenum carbide, β-Mo2 C (35-0787). The sample with
R/Mo =R/Mo
5 was = characterized by the maximum
5 was characterized intensity
by the maximum of reflections
intensity of the β-Mo
of reflections of the2Cβ-Mo
phase
2 C phase
and theandlowest intensity
the lowest of reflections
intensity of free of
of reflections carbon (see Figure
free carbon 5a). This
(see Figure 5a).indicated the
This indicated the
completeness of the carbide
completeness formation
of the carbide from itsfrom
formation precursors. An increase
its precursors. in the reducing
An increase in the reducing
agent content led to the
agent content ledappearance of η-MoC
to the appearance and an and
of η-MoC increase in free amorphous
an increase carbon.carbon.
in free amorphous
The results are in good agreement with the phase diagram, according
The results are in good agreement with the phase diagram, according to which η-MoC to which η-MoC is is
formedformed
in the presence of the excess carbon [37].
in the presence of the excess carbon [37].
DiffuseDiffuse
reflections in theindiffractogram
reflections the diffractogram indicate
indicatehighhighdispersion
dispersionofofthethe material,
material, which,
which, in
in this
this case,
case,could
couldbe beprovided
providedfor foruniform
uniformdistribution
distributionofof molybdenum
molybdenum carbide
carbide particles
particles over
over a carbon
a carbon matrix.
matrix.
The phaseThecomposition
phase compositionof the samples synthesized
of the samples using hydroquinone
synthesized was repre-
using hydroquinone was repre-
sented sented
by twoby compounds: α-Mo C (35-0787) and γ-MoC (45-1015)
two compounds: α-Mo2 C (35-0787) and γ-MoC (45-1015) (Figure 5b).
2 (Figure 5b). At the At the
lowest lowest
reducing agent content
reducing (R/Mo (R/Mo
agent content = 4), the= predominant
4), the predominantphase wasphaseα-Mo
was2C, and2 C,
α-Mo an and an
increaseincrease in theratio
in the molar molar ratioled
R/Mo R/Moto an led to an increase
increase in the γ-MoC
in the γ-MoC content.content. To establish
To establish the the
structure
structure of free carbon
of free carbon presented presented in samples,
in samples, RamanRamanspectraspectra were(Figure
were used used (Figure
6). 6).

1500
Intensity, a.u.

1000

500

0
Nanomaterials 2021, 11, x FOR PEER REVIEW 1000 1200 1400 1600 1800 2000 9 of 16
Raman shift, сm−1
(a)

8000
Intensity, a.u.

6000

4000

2000

0
1000 1200 1400 1600 1800 2000
Raman shift, сm−1
(b)
Figure 6. Raman
Figure spectra spectra
6. Raman of a sample of molybdenum
of a sample blue xerogels
of molybdenum obtained
blue xerogels using (a)
obtained glucose
using (G-
(a) glucose (G-7)
7) and (b) hydroquinone (H-4) calcined at 900 ° C in◦ inert N 2 atmosphere.
and (b) hydroquinone (H-4) calcined at 900 C in inert N atmosphere.
2

Figure Figure
6 shows that the
6 shows spectrum
that in the in
the spectrum region of 500–2500
the region cm−1 contains
cm−1 contains
of 500–2500 two peaks,
two peaks,
1591 and 1336
1591 andcm1336 cm−1 , characteristic
−1, characteristic of the of
disordered structure
the disordered of carbon
structure materials.
of carbon A nar-
materials. A narrow
row and clear
and clearpeak
peakat 1582 cmcm
at 1582 −1 − 1
is characteristic of a single
is characteristic crystal
of a single of graphite
crystal (G-line).
of graphite For For
(G-line).
disordered
disordered structures,
structures, this
this line line is blurred
is blurred and one and oneline
more more line appears
appears at lowerat values
lower values
of the of the
shift (D-line)
shift (D-line) [38].
[38]. The The intensity
intensity ratio ofratio of lines,
these these Ilines, ID /IG , enables
D/IG, enables calculating
calculating the degree
the degree of of
orderingordering in the carbon
in the carbon material.
material. In the studied
In the studied samples,samples, thiswas
this ratio ratio was
1.15 and1.15 and
1.20 for1.20 for
glucose and hydroquinone, respectively, indicating a low ordering in the studied carbon
material. Thus, molybdenum carbide contains amorphous carbon, as confirmed by XRD
data and Raman spectroscopy.
 7) and (b) hydroquinone (H-4) calcined at 900 °C in inert N2 atmosphere.

Figure 6 shows that the spectrum in the region of 500–2500 cm−1 contains two peaks,
1591 and 1336 cm−1, characteristic of the disordered structure of carbon materials. A nar-
Nanomaterials 2021, 873 clear peak at 1582 cm is characteristic of a single crystal of graphite (G-line). For
row11,and −1
8 of 14
disordered structures, this line is blurred and one more line appears at lower values of the
shift (D-line) [38]. The intensity ratio of these lines, ID/IG, enables calculating the degree of
ordering in the carbon material. In the studied samples, this ratio was 1.15 and 1.20 for
glucose andrespectively,
glucose and hydroquinone, hydroquinone, respectively,
indicating indicatinginathe
a low ordering lowstudied
ordering in the studied carbon
carbon
material. Thus, molybdenum carbide contains amorphous
material. Thus, molybdenum carbide contains amorphous carbon, as confirmed by XRD carbon, as confirmed by XRD
data and
data and Raman spectroscopy. Raman spectroscopy.

3.3. Molybdenum
3.3. Molybdenum Carbide Carbide Characterization
Characterization
The morphology of the synthesized molybdenum carbide samples was analyzed using
The morphology of the synthesized molybdenum carbide samples was analyzed us-
scanning electron microscopy. Figure 7 shows micrographs of Mo2 C particles obtained by
ing scanning electron microscopy. Figure 7 shows micrographs of Mo2C particles obtained ◦
heat treatment of molybdenum blue xerogels in an inert atmosphere at 900 C.
by heat treatment of molybdenum blue xerogels in an inert atmosphere at 900 °C.

als 2021, 11, x FOR PEER REVIEW 10 of 16

(a) (b)

(d)
(c)

Micrographs
Figure 7.Figure of Mo2 C of
7. Micrographs obtained by heat treatment
Mo2C obtained of a molybdenum
by heat treatment blue xerogel
of a molybdenum bluesynthesized using (a,b) glucose
xerogel synthe-
sized using (a,b) glucose (G-5, R/Mo = 5) and
(G-5, R/Mo = 5) and (c,d) hydroquinone (H-4, R/Mo = 4). (c,d) hydroquinone (H-4, R/Mo = 4).

Figure 7a,b showFigure 7a,b

that the show that the
molybdenum molybdenum
carbide samples carbide samples (G-5)
(G-5) contained sharpcontained
par- sharp parti-
cles with clear edges. On the fragment surface, smaller, irregular-shaped
ticles with clear edges. On the fragment surface, smaller, irregular-shaped particles were particles were
observed. Highly dispersed particles of molybdenum carbide
observed. Highly dispersed particles of molybdenum carbide were distributed in the car- were distributed in the
bon matrix, which carbon
led tomatrix, which led of
broad reflections tomolybdenum
broad reflections of molybdenum
carbide carbide
in the diffraction pat-in the diffraction
patterns
terns of the samples of the using
synthesized samples synthesized
glucose. using glucose.
The predominant size ofThe predominant
primary molyb- size of primary
molybdenum
denum carbide particles enclosedcarbide particles
in the carbon enclosed
matrix in the
was 400 nm.carbon matrix
It should was 400
be noted thatnm. It should be
the same morphology was observed for all investigated samples of carbides, synthesized
using glucose (G-4–G-9).
Figure 7c,d show photomicrographs of molybdenum carbide obtained by heat treat-
ment of a molybdenum blue xerogel synthesized using hydroquinone. Most of the objects
in the field of view were aggregates of primary molybdenum carbide particles with irreg-

Nanomaterials 2021, 11, 873
Figure 7a,b show that the molybdenum carbide samples (G-5) contained sharp par-
ticles with clear edges. On the fragment surface, smaller, irregular-shaped particles were
observed. Highly dispersed particles of molybdenum carbide were distributed in the car-
bon matrix, which led to broad reflections of molybdenum carbide in the diffraction pat- 9 of 14
terns of the samples synthesized using glucose. The predominant size of primary molyb-
denum carbide particles enclosed in the carbon matrix was 400 nm. It should be noted that
the same morphology was observed for all investigated samples of carbides, synthesized
usingnoted
glucosethat the same morphology was observed for all investigated samples of carbides,
(G-4–G-9).
synthesized
Figure 7c,d show usingphotomicrographs
glucose (G-4–G-9).of molybdenum carbide obtained by heat treat-
ment of a molybdenum bluephotomicrographs
Figure 7c,d show xerogel synthesized ofusing
molybdenum carbideMost
hydroquinone. obtained
of theby heat treat-
objects
ment of a molybdenum blue xerogel synthesized using hydroquinone. Most
in the field of view were aggregates of primary molybdenum carbide particles with irreg- of the objects
in the field of view were aggregates of primary molybdenum carbide
ular shape and diameter not more than 1 μm. In contrast to samples obtained with excess particles with ir-
regular
glucose, shape and
the sample under diameter not more
consideration than 1 µm.
contained In contrast
a small number ofto fragment-like
samples obtained par- with
excess glucose, the sample under consideration contained a small number
ticles of amorphous carbon. An increase in the carbon content in samples H-5/H-9 leads of fragment-like
to an particles of amorphous
insignificant change in thecarbon. An increase
morphology of thein the carbon
samples content
according in samples
to SEM results.H-5/H-9
leads to an insignificant change in the morphology of the samples according
To determine the characteristics of the porous structure, we performed low-temper- to SEM results.
To determine the characteristics of the porous structure, we performed
ature adsorption of N2; the adsorption and desorption isotherms are shown in Figure 8. low-temperature
adsorption of N2 ; the adsorption and desorption isotherms are shown in Figure 8.

3
3 Adsorption
Adsorption, mmol/g

Adsorption, mmol/g
Desorption

2
2

1
1
Nanomaterials 2021, 11, x FOR PEER REVIEW 0 11 of 16
0 0.0 0.5 1.0 1.5 2.0
0.0 0.2 0.4 0.6 0.8 1.0 t, nm
P/Ps (b)
(a)

Adsorption
Adsorption, mmol/g
Adsorption, mmol/g

Desorption 4
4
3
3 2

2 1
0
0.0 0.5 1.0 1.5 2.0
1 t, nm
0.0 0.2 0.4 0.6 0.8 1.0
P/Ps (d)
(c)

Figure 8. (a,b) Nitrogen adsorption isotherms and (c,d) t-plots of Mo2 C synthesized from molyb-
Figuredenum
8. (a,b)blue
Nitrogen adsorption
xerogels isotherms
(calcined and
at 900 ◦ C in (c,d) t-plots
an inert of Mo2C synthesized
atmosphere) from(G-5,
using glucose molyb-
R/Mo = 5)
denum blue xerogels (calcined at 900 °C in an inert
(a,b) and hydroquinone (H-4, R/Mo = 4) (c,d). atmosphere) using glucose (G-5, R/Mo = 5)
(a,b) and hydroquinone (H-4, R/Mo = 4) (c,d).
The adsorption isotherms of molybdenum carbide samples (G-5, H-4) belonged to
The
typeadsorption
IV, accordingisotherms of molybdenum
to the Brunauer carbide
classification, samples
which (G-5, H-4) belonged
is characteristic to
of polymolecular
type IV, according to the Brunauer classification, which is characteristic of
adsorption—capillary condensation in mesopores. The shape of the hysteresis loop was ofpolymolecular
adsorption—capillary condensation
type H3, corresponding in mesopores.
to the presence of slit The shape
pores. of initial
In the the hysteresis
section ofloop was
the isotherm,
of type
weH3, corresponding
observed to the presence
a sharp increase of slit pores.
in adsorption, In the
indicating theinitial section
presence of the iso- The
of micropores.
therm, we observed
adsorption a sharp
isotherm increase in
presented in adsorption,
the coordinatesindicating the presence
of the t-method hadof micropores.
three characteristic
The adsorption
sections corresponding to the adsorption in micro-, meso-, and macropores. charac-
isotherm presented in the coordinates of the t-method had three
teristic sections corresponding
The pore to the adsorption
size distribution calculated by in micro-,
the BJHmeso-,
method and(for
macropores.
mesopores) and the
The pore size distribution
Horvath–Kawazoe method calculated by theisBJH
(for micropores) shownmethod (for 9.mesopores)
in Figure The sampleand hadthe
a rather
Horvath–Kawazoe
narrow pore sizemethod (for micropores)
distribution, and the is shown indiameters
prevailing Figure 9. The (slitsample had a rather
pore width) were 4 and
narrow pore size distribution, and the prevailing diameters (slit pore width) were 4 and 1
1 nm.
nm.
Molybdenum carbide samples obtained by heat treatment of molybdenum blue xero-
gels synthesized using glucose at different R/Mo molar ratios were investigated in a sim-
ilar way. For all investigated samples, isotherms similar to those shown in Figure 8 were
obtained.
The characteristics of the porous structures of the samples are shown in Table 1.

0.06
0.015
 narrow pore size distribution, and the prevailing diameters (slit pore width) were 4 and 1
nm.
Molybdenum carbide samples obtained by heat treatment of molybdenum blue xero-
gels synthesized using glucose at different R/Mo molar ratios were investigated in a sim-
ilar way. For all investigated samples, isotherms similar to those shown in Figure 8 were
Nanomaterials 2021, 11, 873 obtained. 10 of 14
The characteristics of the porous structures of the samples are shown in Table 1.

0.06
0.015

dV|dd, сm3/g nm
dV|dd, сm3/g nm
0.04
0.010

0.005 0.02

0.000
Nanomaterials 2021, 11, x FOR PEER REVIEW
5 10 15 0.8 1.2 1.6 2.012 of 16
Pore diameter, nm Pore diameter, nm
(a) (b)
0.08
dV|dd, сm3/g nm

dV|dd, сm3/g nm
0.06 0.08

0.04

0.04
0.02

5 10 15 0.8 1.2 1.6 2.0

Pore diameter, nm Pore diameter, nm
(c) (d)
Figure 9. Meso- (a,c) and micropore (b,d) size distribution of molybdenum carbide synthesized from
Figure 9. Meso- (a,c) and micropore (b,d) size distribution of molybdenum carbide synthesized
frommolybdenum
molybdenum blueblue
xerogels usingusing
xerogels (a,b) glucose (G-5, R/Mo
(a,b) glucose (G-5,=R/Mo
5) and (c,d) hydroquinone
= 5) and (H-4, R/Mo (H-4,
(c,d) hydroquinone
R/Mo= 4),=calcined at 900at°C900
4), calcined ◦
in anCinert
in anatmosphere.
inert atmosphere.

Molybdenum
The specificcarbide
surface samples
area (totalobtained by heat
and internal) andtreatment
pore volumeof molybdenum
of micropores blue
in- xe-
creased
rogels with an increase
synthesized in the reducing
using glucose agent
at different content.
R/Mo molarThe ratios
main contributor to these in a
were investigated
characteristics
similar way. For was amorphous carbon.
all investigated samples, isotherms similar to those shown in Figure 8
Thus, the synthesized molybdenum carbide samples have a bimodal porous struc-
were obtained.
ture.
The Microporosity
characteristicsis of
due to porous
the the presence of amorphous
structures carbon, and
of the samples mesoporosity
are shown with
in Table 1.
a predominant diameter around 4 nm corresponds to the structure of molybdenum car-
bide, in which pores are formed due to sintering of primary particles. A similar porous
Table 1. Characteristics of the porous structure of Mo2 C synthesized from molybdenum blue xerogels using glucose and
structure is observed in the synthesis of molybdenum carbide using ascorbic acid as a
hydroquinone with different R/Mo molar ratios, calcined at 900 ◦ C in an inert atmosphere.
carbon source [32].
Parameters
Table 1. Characteristics of the porous structure of Mo2C synthesized from molybdenum blue xero-
Molar Ratio
Sample
(R/Mo)
Sgels
a (BET), ∑V,
using glucose and Vmeso
hydroquinone (BJH),
with V0 (DR),
different R/Mo molar ratios, V t , (t-plot)
calcined dp ,
at 900 °C in an
m2 /g
inert atmosphere. cm3 /g cm3 /g cm3 /g cm3 /g nm
Glucose Parameters
G-4 4.0 7.1 V0 Vt, 4; 1
Molar0.011
SampleRatio (R/Mo) 0.007 Sa (BET), 0.003 Vmeso (BJH),0.001
∑V, dp,
G-5 5.0 130.90.097 0.036 2 0.052 (DR),
0.026 (t-plot) 4; 1
m /g сm3/g сm3/g nm
G-7 7.0 174.90.079 0.001 0.071 0.046
сm3/g сm3/g 4; 1
Hydroquinone Glucose
H-4 4.0 G-4
203.0 4.0
0.150 0.0797.1 0.011
0.082 0.007 0.043 0.003 0.001 4;4;11
G-5 5.0 130.9 0.097 0.036 0.052 0.026 4; 1
Sa —specific surface area calculated using BET equation, ΣV—the total specific pore volume, Vmeso —mesopore volume, V0 —the micropore
G-7
volume determined based on the Dubinin–Radushkevich 7.0
equation. Vt —value174.9 0.079
of micropore 0.001 using
volume calculated 0.071 0.046de Boer
the t-plot 4; 1
method, dp —predominant pore size. Hydroquinone
H-4 4.0 203.0 0.150 0.079 0.082 0.043 4; 1
The specific surface area (total and internal) and pore volume of micropores increased
Sa—specific surface area calculated using BET equation, ΣV—the total specific pore volume, Vmeso—
with an increase in the reducing agent content. The main contributor to these characteristics
wasmesopore
amorphous volume, V0—the micropore volume determined based on the Dubinin–Radushkevich
carbon.
equation. Vt—value
Thus, the of micropore
synthesized volume calculated
molybdenum carbideusing the t-plot
samples de Boer
have method, porous
a bimodal dp—predomi-
structure.
Microporosity
nant pore size. is due to the presence of amorphous carbon, and mesoporosity with a
predominant diameter around 4 nm corresponds to the structure of molybdenum carbide,
3.4. Catalytic Activity of Molybdenum Carbides
Molybdenum carbide samples obtained by thermal decomposition of molybdenum
blue xerogels, characterized by different phase compositions (Table 2) were tested as a
catalyst during the dry reforming of methane. The reaction was carried out in a tempera-
ture range of 800 °C–870 °C. H2, CO, and H2O were found among the reaction products.
Nanomaterials 2021, 11, 873 11 of 14

in which pores are formed due to sintering of primary particles. A similar porous structure
is observed in the synthesis of molybdenum carbide using ascorbic acid as a carbon
source [32].

3.4. Catalytic Activity of Molybdenum Carbides

Molybdenum carbide samples obtained by thermal decomposition of molybdenum
blue xerogels, characterized by different phase compositions (Table 2) were tested as a
catalyst during the dry reforming of methane. The reaction was carried out in a temperature
range of 800 ◦ C–870 ◦ C. H2 , CO, and H2 O were found among the reaction products.

Table 2. Catalytic
Nanomaterials activity
2021, 11, x FOR of Mo2 C synthesized from molybdenum blue xerogels using glucose (R/Mo
PEER REVIEW 13 of 16= 7) and hydro-
quinone (R/Mo = 4).

Parameters
Table 2. Catalytic activity of Mo2C synthesized from molybdenum blue xerogels using glucose
Reducing
(R/MoAgent,
= 7) and hydroquinone (R/Mo = 4).
Sample
(R/Mo)
Phase Sa (BET) *, k900 , ks 900 ,
Composition m 2 /g s−1 s−1 m−2
Parameters
Reducing Agent,
Glucose, Phase Sa (BET) *, k900, ks900,
Sample (R/Mo)
composition m2/g s−1 s−1m−2
G-7 7 α-Mo2 C, η-MoC, C 56 1.25 0.05
Glucose,
Hydroquinone
G-7 7 α-Mo2C, η-MoC, C 56 1.25 0.05
H-4 4 α-Mo2 C, γ-MoC
Hydroquinone 25 2.30 0.10
H-4 4 α-Mo C,◦γ-MoC
900 25 2.30 0.10
* Sa , specific surface area after conversion; k900 , constant rate calculated at 900 C; ks , constant rate related to surface area of catalyst.
2

* Sa, specific surface area after conversion; k900, constant rate calculated at 900 °C; ks900, constant
rate related to surface area of catalyst.
The temperature dependencies of the conversions of starting materials (CH4 and CO2 )
are The
shown in Figure
temperature 10, in addition
dependencies to the Hof
of the conversions 2 /CO ratio,
starting which
materials (CHindicates
4 and
the selectivity
of 2the
CO ) are catalysts under
shown in Figure study.
10, in The
addition catalyst
to the obtained
H2/CO ratio, which from molybdenum
indicates the selectivity blue synthesized
of the catalysts
using under study.
hydroquinone hadTheacatalyst
higherobtained
catalyticfromactivity
molybdenum ◦ C,
blue
at 870 synthesized
a conversion close to 90%
using hydroquinone had a higher catalytic activity
was observed, with the highest H2 /CO molar ratio. at 870 °C, a conversion close to 90%
was observed, with the highest H2/CO molar ratio.

G-7 G- 7
100 H-4 100 H-4

80 80
X CO2, %
X CH4, %

60 60

40 40

20 20

0 0
800 820 840 860 880 800 820 840 860 880
0
0
Temperature, C Temperature, C
(a) (b)
G-7
1,0 H-4

0,8

0,6
H2/CO

0,4

0,2

0,0
800 820 840 860 880
0
Temperature, C
(c)
Figure 10. Effect of the phase composition of the catalyst on (a) CH4 conversion, (b) CO2 conver-
Figure 10. Effect of the phase composition of the catalyst on (a) CH4 conversion,
sion, and (c) H2/CO ratio for dry reforming of methane. For all experiments, the flow rate of the
(b) CO2 conversion,
and (c) H /CO ratio for dry reforming of methane.
2 30 cm /min and the contact time was 0.6 s.
gas mixture was 3 For all experiments, the flow rate of the gas
3
mixture was 30 cm /min and the contact time was 0.6 s.
To compare the obtained results, based on kinetic experiments, we determined the
rate constant and specific rate constant per unit surface of the catalyst (Table 2). The mo-
lybdenum carbide sample, represented by two phases (α-Mo2C and γ-MoC), was more
Nanomaterials 2021, 11, 873 12 of 14

To compare the obtained results, based on kinetic experiments, we determined the

rate constant and specific rate constant per unit surface of the catalyst (Table 2). The
molybdenum carbide sample, represented by two phases (α-Mo2 C and γ-MoC), was more
active. The sample with a different phase composition (α-Mo2 C and η-MoC) has the
specific rate constant two-times lower.

4. Discussion
The traditional method of producing molybdenum carbides is the TPRe based on the
effect of a gas mixture (Cn H2n+2 /H2 ) on MoO3 . Using CH4 /H2 and C2 H6 /H2 mixtures
leads to the formation of one phase of β-Mo2 C [17,37–40]. The formation of monocarbides
(MoC) is possible using hydrocarbons with a long chain of aromatic compounds [9,17].
There is practically no literature on α-Mo2 C synthesis by the TPRe.
This study presented the results of molybdenum carbide synthesis by a simple method
based on obtaining molybdenum blue dispersions and subsequently drying and heat-
treating them in an inert atmosphere. By changing the reducing agent during molybdenum
blue dispersion synthesis, it is possible to form different phases of molybdenum carbides.
This synthesis method is flexible and scalable and can be considered an alternative to the
traditional TPRe.
In this paper, we reported molybdenum carbide synthesis using glucose and hydro-
quinone. The phase composition of molybdenum carbides depends on the type and content
of the organic reducing agent. When glucose is used, α-Mo2 C and η-MoC are formed, and
the ratio between them is determined by the amount of glucose: with minimum glucose,
monophase samples are formed (Mo2 C), and increasing the glucose content increases the
amount of η-MoC. When hydroquinone is used, the presence of two phases is observed
in the entire investigated range of the R/Mo molar ratio: α-Mo2 C and γ-MoC. It should
be noted that in our previous study it was shown that the use of ascorbic acid leads to the
formation of a mixture of Mo2 C and η-MoC carbides, as well as when glucose is used [32].
The chosen strategy for the synthesis of carbides refers to the method of obtaining a
solid–liquid phase, in which organic compounds are used as a carbon source [9]. Table 3
summarizes the main properties of molybdenum carbide synthesized using a different
liquid phase carbon source. This approach allows varying the content of the organic
reducing agent, as in the case of the urea “solution” route, which leads to a change in the
phase composition of the resulting carbide and a change in the specific surface area from
12 to 22 m2 /g [26]. However, in the case of using urea, molybdenum nitrite is also formed
in addition to molybdenum carbide.

Table 3. Phase composition and BET surface area of molybdenum carbide with different liquid carbon sources.

Carbon Source Glucose Hydroquinone Ascorbic Acid [32] Sucrose [27] Urea [26]
[R]/[Mo] 4–7 4 0.6–5 2–3.1 1–7
α-Mo2 C; α-Mo2 C; β-Mo2 C;
Mo2 C γ-Mo2 N;
Phase composition η-MoC; γ-MoC; η-MoC;
MoC1− x α-Mo2 C
C C C
Sa (BET),
7.1–175.0 203.0 1.4–63.0 5 12.0–22.0
m2 /g

Comparing our results with previous studies with similar synthesis method, using a
molybdenum salt and a liquid-phase carbon source (5 m2 /g sucrose) [27], we found that,
when using molybdenum blue dispersions as precursors, molybdenum carbides with a
higher surface area (7.1–203 m2 /g) are formed.
For the first time, samples containing γ-MoC were obtained and their activity during
the carbon dioxide conversion of methane was established. The molybdenum carbide
samples obtained in this study show high catalytic activity in the DRM reaction. Samples
representing a mixture of phases have greater activity and selectivity in this reaction.
Nanomaterials 2021, 11, 873 13 of 14

5. Conclusions
In this work, we developed a simple method for obtaining molybdenum carbides using
dispersions of molybdenum blue and organic compounds (glucose and hydroquinone) as
a carbon source. The ability to vary the type and content of the organic reducing agent
makes it possible to synthesize molybdenum carbide of various phase composition and
porous structure.
It has been shown that when glucose is used, α-Mo2 C and η-MoC are formed, while
when using hydroquinone, α-Mo2 C and γ-MoC are formed.
The porous structure of the samples is represented by meso- and micropores, the
specific surface area is in the range of 7.1–203 m2 /g.
Samples of carbides were tested in the reaction of dry reforming of methane in the
temperature range 800–890 ◦ C. It was shown that a sample of a mixture of molybdenum
carbides α-Mo2 C and γ-MoC exhibits the highest catalytic activity.
The developed method for the synthesis of molybdenum carbides makes it possible to
obtain bulk and supported catalysts based on molybdenum carbide by the sol-gel method.

Author Contributions: Conceptualization, N.G. and V.S.; methodology, N.G. and M.M.; investi-
gation, N.G. and M.M.; data curation, N.G. and V.S.; writing—original draft preparation, N.G.;
writing—review and editing, N.G., M.M., V.N., and V.S.; supervision, V.N. and V.S. All authors have
read and agreed to the published version of the manuscript.
Funding: This research was funded by D. Mendeleev University of Chemical Technology (grant no.
031-2020).
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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