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Catalysis Today 333 (2019) 36–46

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Oxygen pathways in oxidative coupling of methane and related processes. T


Case study: NaWMn/SiO2 catalyst

Mikhail Sineva, , Ekaterina Ponomarevaa, Ilya Sinevb,1, Vladimir Lomonosova, Yury Gordienkoa,
Zukhra Fattakhovaa, Dmitry Shashkina
a
Semenov Institute of Chemical Physics, R.A.S., 119991 Moscow, Russia
b
Laboratory of Industrial Chemistry, Ruhr-University Bochum, 44801 Bochum, Germany

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

Keywords: The chemical complexity of processes that accompany the oxygen turnover during the high-temperature se-
Light alkanes lective oxidation processes, such as oxidative coupling of methane (OCM), oxidative dehydrogenation and
High-temperature selective oxidation oxidative cracking of light alkanes is analyzed. Particularly, chemical reactions and phase transitions in the
Oxide catalysts complex oxide OCM catalyst NaWMn/SiO2 are studied using the X-ray photoelectron spectroscopy, X-ray
Oxidative coupling methane
powder diffraction, and scanning electron microscopy combined with local elemental analysis. It was found that
NaWMn/SiO2catalyst
during oxygen desorption crystalline Na2WO4 and Mn2O3 phases disappear, and newly-formed compounds so-
Oxygen turnover
Phase transitions lidify in the form of crystalline MnWO4 and the glue-like matter. The latter contains sodium and most likely
Mn2+ ions. Its localization on the grain boundaries of the SiO2 (α-cristobalite) bulbs and morphology indicate
that this matter is amorphous and has a high adhesion to the silica surface. After re-oxidation, the phase
composition of the sample restores, although the size and location of the restored Na2WO4 and Mn2O3 particles
evidence for their formation from the glue-like matter or its molten precursor. It was concluded that the sup-
ported components are present during the oxygen turnover in a molten state, in which all chemical and mass-
transfer processes are accelerated.

1. Introduction products, reaction kinetics.


The mentioned processes have some similarities in the optimal
When considering the mechanisms of selective partial oxidation of conditions (they efficiently proceed at temperatures as high as 700 °C
organic substances, light alkanes (LA) in particular, the main attention and above) and in the reaction mechanism, including the alkane mo-
is paid, as a rule, to the activation of the initial organic molecules and lecule activation and contribution of free-radical chemistry to the for-
their further transformations. However, the activation of the second mation of the final products. Also, several new phenomena related to
reactant, i.e. the oxidant, primarily molecular oxygen, and its reaction the role of active oxygen species have been revealed. This required
pathways are also of great importance. Different types of oxygen species some revision of the existing notions about the activation of molecular
participate in all steps of catalytic oxidation and, thus, their properties oxygen, including the key factors that govern its interaction with sur-
determine both the rate and selectivity of the overall process. Various face active sites and involvement into the catalytic cycle.
factors that determine such properties are discussed in the fundamental In many cases the kinetics of the processes under consideration can
monograph [1]. be described in the framework of so-called redox, or Mars-van Krevelen
During the last decades the processes of LA direct transformation scheme. In the classical Mars-van Krevelen model [2], the overall redox
into value-added products, such as oxidative coupling of methane process is represented as a cycle consisting of two reactions, namely,
(OCM), oxidative dehydrogenation (OD) of C2+ and oxidative cracking reduction and re-oxidation of the O-containing active sites:
(OC) of C3+ alkanes have been extensively studied with the emphasis
on the development of efficient catalysts and on the mechanistic as- [O] + A® […] + AO (1)
pects, such as the elucidation of the nature of surface active sites, al-
kane molecule activation and pathways of their transformation to final […] + O2 ®2[O] (2)


Correspondence author.
E-mail address: mysinev@rambler.ru (M. Sinev).
1
Current address: Experimental Physics IV, Ruhr-University Bochum, 44801 Bochum, Germany.

https://doi.org/10.1016/j.cattod.2018.06.028
Received 18 December 2017; Received in revised form 16 April 2018; Accepted 15 June 2018
Available online 18 June 2018
0920-5861/ © 2018 Published by Elsevier B.V.
M. Sinev et al. Catalysis Today 333 (2019) 36–46

where [O] and […] are oxidized and reduced states of an active site, A product (ethane) forms. We concluded in [9] that if the oxygen binding
and AO are the initial molecule and the product of oxidation. energy is significant and reaction (4) does not proceed, or its equili-
In reality, however, very few processes (such as CO oxidation) can brium is shifted to the left, a different mechanism, namely so-called
be literally described by these two reactions. Moreover, the catalyst re- 'oxidative dehydrogenation route', can lead to the active site re-oxida-
oxidation reaction (2) cannot be considered as 'elementary' because it tion via the following steps:
requires the participation of two reduced sites (which as a rule are
[OH]+O2 ® [O] + HO•2 (5)
distant in real catalysts) and the transfer of multiple electrons. In other
words, such oversimplified writing of the reaction scheme only de- [OH] + HO•2® [O]+H2 O2 (6)
termines the shape of the kinetic equation that describes that rate of the
product AO formation (WAO) in the steady state H2 O2 ®2 OH• (7)

kred PAm × kox POn2 [OH] + OH•® [O]+H2 O (8)


WAO =
kred PAm + kox POn2 (1) All four reaction in this sequence can be considered as elementary,
or and their kinetic constants can be estimated based on the existing
thermochemical data [10–13]. Our estimates demonstrate that for the
WAO = kredΘP m
A (1a) majority of the OCM catalysts reaction (5) is the rate-determining step
and in the active site re-xidation and also determines the first order with
n
respect to oxygen pressure in the framework of the Mars-van Krevelen-
Θ = k ox PO2/(kredP m n
A + k ox P O2) (1b) type description (i.e., n = 1), which is usually observed experimentally,
where PA and PO2 are pressures of the substrate and molecular oxygen; but can be hardly explained in the framework of the 'dehydroxylation-
kred and kox are rate constants of reactions (1) and (2); m and n are type' reaction mechanism. The same scheme of reoxidation via the
kinetic orders of reactions (1) and (2); Θ is the degree of oxidation of 'oxidative dehydrogenation' of the surface hydroxy-groups was suc-
the catalyst active sites, i.e. their fraction present in oxidized state in cessfully applied for the analysis of the OC kinetics [14]. This example
the steady-state reaction conditions. demonstrates that the same formal kinetic equation (particularly, Mars-
The above reasoning assumes that all other processes are not kine- van Krevelen type) can fairly well describe the behavior of reacting
tically relevant. systems of very different chemical nature.
Herewith, two important circumstances should be taken into ac- It is important to notice that the same reaction, e.g., OCM, can be
count: heterogeneous-homogeneous (in terms of the nature of key inter-
mediates – free radicals – and of the localization of their formation and
(i) unlike the catalysts for total oxidation and partial oxidation of non- transformations both on the catalyst surface and in the gas phase) and
saturated hydrocarbons and functionalized organic compounds, redox-type (in terms of the functioning of the catalyst active sites), and
most of the efficient catalysts for OCM, OD and OC do not contain these two aspects of its mechanism are complementary.
precious and transition metals; A complex oxide system of the general formula Na2WO4/MnOX/
(ii) the main target organic products formed in the LA reactions con- SiO2, or NaWMn/SiO2 is known as one of the most efficient OCM cat-
sidered here do not contain oxygen. alysts and also is very active and selective in the ethane ODH. This
catalyst was first suggested by X.P. Fang, S.B. Li, and co-workers [15].
Indeed, in all three processes (OCM, OD, OC) the number of hy- Although it has been extensively studied by several research groups,
drogen atoms in the organic products is less than in the initial LA many aspects of its functioning are still insufficiently understood [16].
molecule, and the remaining hydrogen atoms are bound with oxygen in Unlike many other catalysts used for the LA high-temperature oxi-
the water molecule in the course of the reaction. In other words, in spite dations (OCM, OD, OC), this one contains two elements (Mn and W)
of the satisfactory description of the process kinetics by Eq. (1), the set that form O-containing compounds in different oxidation states and,
of reactions (1) and (2) obviously does not fully reflect its chemical thus, can possess various types of reactive oxygen. It was demonstrated
nature. Beginning with the classical work of K.-I. Aika and J.H. Luns- recently [17] that the equations of Mars-van Krevelen type successfully
ford [3], it is generally accepted that the mechanism of the LA molecule describe the kinetics of OCM and ethane OD over NaWMn/SiO2. Also,
activation consists in the homolytic cleavage of one C-H-bond accom- as a typical redox catalyst, it produces OCM products with high se-
panied by the formation of a free alkyl radical R and a surface OH- lectivity while reacting with methane as a reducing agent [18,19]. Its
group: reduction with hydrogen is accompanied by the water formation [19].
After reduction it can be subsequently re-oxidized with molecular
[O] + RH® [OH]+R• (3)
oxygen. Our data show that this mixed oxide contains two forms of
This means that the overall process of regeneration (re-oxidation) of reactive oxygen characterized by different concentrations, lifetimes,
active sites consists of a reaction sequence that starts with a reduced (H- and reactivity [19]. The kinetic estimates demonstrate that the form
containing) state [OH] and ends with an oxidized form of the active site that is present in a lower concentration and has a shorter lifetime in the
[O]. In the simplest sequence of such kind the first reaction step is absence of gaseous O2 (called 'weakly-bonded oxygen') is much more
dehydroxylation: reactive and most probably this form is responsible for the catalytic
activity in the steady-state regime. The direct calorimetric measure-
[OH] ® [O]+[…]+H2 O (4)
ments allowed us to assign the release and uptake of this weakly-
Combination of reactions (4) and (2) is accepted by many authors as bonded oxygen to the Mn3+ ↔ Mn2+ redox transition [20].
the sequence of steps that leads to the catalyst re-oxidation [4–7]. In this work, we attempted to shed light on the chemical nature of
However, one should take into account that reaction (4) is strongly the processes responsible for the redox behavior of the NaWMn/SiO2
endothermic and reversible, and high concentration of water in the catalyst. We focused on studying the turnover of the weakly-bound
reaction mixture in the conditions of OCM, OD and OC reactions may oxygen, namely its release (desorption in a vacuum or in an inert gas)
cause a strong shift of its equilibrium to the left. Our experiments de- and uptake (reoxidation). For this purpose, based on our previous data
monstrated [8] that even in a flow of inert gas (helium) water is not on the OCM and ethane ODH kinetics [17], oxygen TPD and thermo-
evolved and oxygen vacancies do not form on the surface of Li/MgO (a chamistry of the weakly-bonded oxygen [20] we applied three techni-
'classical' model OCM catalyst) during its reduction with methane ques, namely X-ray photoelectron spectroscopy (XPS), X-ray powder
pulses at temperatures up to 650 °C, although the methane coupling diffraction (XRD), and scanning electron microscopy combined with

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M. Sinev et al. Catalysis Today 333 (2019) 36–46

energy dispersive X-ray spectroscopy (SEM-EDX), to characterize the applied to compensate the charging effects. High-resolution spectra for
chemical and structural changes that accompany the oxygen turnover C 1s, O 1s, Si 2p, Na 1s, W 4f and Mn 2p photoelectron lines were
during the catalytic reaction and oxygen desorption and uptake. recorded. The Si 2p signal of SiO2 was used as an internal energy
standard and attributed to 103.4 eV. The Casa XPS software with a
2. Experimental Gaussian-Lorentzian product function with a mixing ratio 30% and
Shirley background subtraction was used for peak deconvolution. In O
2.1. Catalyst preparation, characterization, and treatments 1s photoemission spectra curve fitting, the peaks were constrained to
have ± 0.2 eV the same full width at half maximum [21]. Atomic ra-
Mixed NaWMn/SiO2 oxide was obtained using an incipient wetness tios were calculated from the XPS intensities corrected to the corre-
impregnation of the Aldrich Davisil grade 646 silica gel with water sponding Scofield photoemission cross-sections.
solutions of sodium tungstate and manganese nitrate with subsequent The UHV setup was equipped with a separate chamber for sample
thermal treatment. The target content of metals was (in wt. %): 0.8 Na, pre-treatment. Therein the heating for oxygen desorption was carried
3.2 W, 2.0 Mn (atomic ratio Na : W : Mn ≈ 2 : 1 : 2). The details of the out (heating to 800 °C at a ramping rate 2.5 K min−1, keeping at this
catalyst synthesis and its testing in the catalytic OCM process are given temperature for 1 h and quenching to room temperature at average
in [19]. pressure 3 × 10-7 mbar), after which the sample was transferred into
In addition to the sample in the 'as-prepared' state (further also the analysis chamber under vacuum. Unfortunately, the design of the
denoted as 'fresh'), the materials after two different treatments were setup did not allow us to re-oxidize the sample inside the same pre-
also studied. The treatment procedures are described below. treatment chamber.

2.1.1. Reaction equilibrated 2.4. Scanning electron microscopy


About 50 mg of NaWMn/SiO2 oxide ('fresh') was placed into a
quartz reactor and purged for 1 h with a flow of methane-oxygen gas The microstructure of the catalysts was studied by scanning electron
mixture (volume ratio 85 : 15) at 860 °C (this temperature is close to the microscopy (SEM) on a Tescan Mira 3 LMU microscope (TESCAN,
optimum for this particular catalyst). The flow rate was varied in order Check Republic) equipped with an energy-dispersive X-ray spectro-
to achieve certain degrees of oxygen conversion, namely ∼50 and > meter (EDX). The micrographs were generally obtained from the
95%. According to the main concept of the Mars-van-Krevelen model, backscattered electron signal which provides material contrast in ima-
the degree of oxidation of the catalyst active sites depends on the ratio ging. The accelerating voltage (5–30 kV), the working distance
of rates of reactions (1) and (2), and the latter depend, in their turn, on (8–18 mm), as well as the scanning time were varied depending on the
oxygen and substance A partial pressures (see Eq. 1b). So, quenching structure and composition of the sample in order to obtain clear and
the catalyst from the reaction mixtures at different degrees of oxygen sharp images without depositing any conductive layer onto the sample
conversion would allow us to see the difference between the states of surface.
the active components at different degrees of oxidation.
3. Results
2.1.2. Oxygen desorption
About 100 mg of NaWMn/SiO2 oxide ('fresh') was placed into a 3.1. Phase composition (XRD data)
quartz reactor and purged with a He flow (20 ml min−1) at 500 °C; then
it was heated to 900 °C (10 K min−1 ramping rate), kept at this tem- Fig. 1 shows the effect of the flow rate on the oxygen conversion and
perature for 30 min, and finally cooled to room temperature in the same C2-selectivity at 860 °C. These data indicate that at low flow rate we can
gas flow. achieve almost full conversion of oxygen, i.e. its concentration ap-
proaches zero. Thus, according to the Eq. 1b the catalyst approaches an
2.1.3. Re-oxidation almost fully reduced state. On the contrary, at high flow rates oxygen
The sample after oxygen desorption was purged with an oxygen concentration remains high, and the catalyst is likely oxidized in the
flow (20 ml min−1) at room temperature; after rising temperature to steady-state reaction conditions.
600 °C (10 K min−1 ramping rate), it was kept at this temperature for The XRD patterns of the samples after different treatments are given
30 min and then cooled to room temperature in the same gas flow. in Fig. 2. In a good agreement with the existing literature data (see, e.g.,
The gases used in this work were supplied by Linde Gas Russia. We [16,19,22–32], the main phases in the as-prepared sample (curve 1) are
used helium grade A/4.5 (99.995% purity) and oxygen grade 3.5 α-cristobalite, Na2WO4, and Mn2O3. After quenching from the reaction
(99.95% purity). conditions at low degree of oxygen conversion, no significant changes

2.2. Powder x-ray diffraction

The phase composition of the samples before and after various


treatments was studied at room temperature by powder X-ray diffrac-
tion using DRON-2 diffractometer (Cu Kα radiation wavelength
0.154 nm, 2θ angle variation range 8-50°).

2.3. XPS measurements

X-ray photoelectron spectroscopy (XPS) measurements were carried


out at room temperature and the base pressure in the chamber main-
tained at about 5 × 10−10 mbar. An ultra-high vacuum (UHV) setup
was equipped with a monochromatic Al Ka X-ray source
(hν = 1486.6 eV), operated at 14.5 kV and 35 mA, and a high-resolution
Gammadata-Scienta SES 2002 analyzer. The measurements were car-
ried out in the fixed transmission mode with a pass energy of 200 eV Fig. 1. Oxygen conversion (1) and C2-selectivity (2) as a function of the gas
resulting in an overall energy resolution of 0.25 eV A flood gun was flow rate; 860 °C, methane : oxygen = 85 : 15 (vol.).

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M. Sinev et al. Catalysis Today 333 (2019) 36–46

After the thermal treatment, the relative intensity of the low-energy


component increased by a factor of 5.2. This reflects the increase of the
surface concentrations of the supported components (Na, W, Mn), as it
is shown below. Also, two additional components of low intensity ap-
peared in the spectrum at very high electron binding energies (peak
positions between 535 and 537 eV). Their attribution is not discussed
here.

3.2.2. Na 1s line
No visible changes in the position and shape of this line were ob-
served after the treatment. As for the intensity, a very sharp increase
was noticed. The latter can be explained by the substantial increase of
the fraction of the surface covered by Na compounds.

3.2.3. W 4f line
This line is represented by a doublet 35.1–37.3 eV, similar to the
energies earlier reported for WO3 [35,36]. After the vacuum annealing,
a new doublet appears shifted by 2.5 eV to lower electron binding en-
ergies (see Fig. 3b). Its intensity is about 9.5 times lower, whereas the
overall intensity of tungsten signal increases significantly. Earlier si-
Fig. 2. XRD patterns of NaWMn/SiO2 samples: (1) – 'as-prepared'; (2) – after milar electron binding energies were reported for tungsten ions in W4+
quenching from the reaction mixture (oxygen conversion ∼ 50%); (3) – after state [24,25]. It should be noted, however, that if the chemical en-
quenching from the reaction mixture (oxygen conversion > 95%); (4) – after vironment of the W6+ ion changes, the position of their lines can shift
oxygen desorption; (5) – after re-oxidation; description of reflexes: A – SiO2 (α-
by a degree comparable to that observed when their oxidation state
cristobalite), B – Na2WO4, C – Mn2O3, D – MnWO4.
changes [37].

in the XRD patterns were observed (curve 2). However, after quenching
from the reaction mixture at nearly full oxygen consumption, the in- 3.2.4. Mn 2p3/2 l in.s
tensities of the reflexes associated with Na2WO4 and Mn2O3 decrease, Like in the cases of Na and W, the intensity of Mn 2p lines in the XPS
and new reflexes attributed to the MnWO4 phase arise (curve 3). The spectrum increased significantly after the thermal treatment. Moreover,
same changes in the XRD patterns were observed in the sample after as shown in Fig. 4, the relative concentration of manganese (i.e., Mn:Si
oxygen desorption at 900 °C (curve 4). Re-oxidation of the sample after ratio) increased the most significantly – by a factor of 7.7 (compared to
oxygen desorption fully restores its initial phase composition (curve 5). 4.8 and 3.5 in the cases of Na:Si and W:Si ratios). The detailed analysis
Thus, according to the XRD data, phase compositions of the catalyst of this line is associated, however, with substantial difficulties. The
after treatment in the reaction mixture at high oxygen conversion (low most common oxidation states of Mn have significant multiplet splitting
oxygen concentration) and after oxygen desorption at 900 °C in helium and are presented with up to 6 peaks in Mn 2p3/2 l in. The single-to-
flow are very close. On the other hand, the treatment in the reaction noise ratio in our spectra, especially of the untreated sample, is too
mixture at low oxygen conversions (high oxygen concentrations) and small. As a result, neither a detailed deconvolution of Mn2p3/2 l in.s
re-oxidation after oxygen desorption lead to phase compositions which using multiplet structures of possible Mn2+ and Mn3+ states nor an
are similar to the initial ('as prepared') state of the NaWMn/SiO2 analysis of Mn 3 s line can be performed to definitely determine the
system. This allowed us to assume that oxygen turnover processes state of manganese ions. The key spectral feature that allows one to
during the redox treatment (oxygen desorption and re-oxidation) mimic draw a decisive conclusion on the presence of Mn2+ species is the
those that occur during the catalytic reaction. However, during oxygen presence of so-called shake-up satellites around 647.0 eV A similar ar-
desorption and re-oxidation the catalyst surface does not contact with gument was proposed to identify the Mn2+ state in the catalyst after
H- and C-containing molecules and no hydroxylated states and/or C- time-on-stream in the OCM reactor [22].
containing ad-species (or contaminates) can form that could complicate The comparison of two spectra in Fig. 3c (normalized to their peak
the analysis. Thus, namely the redox treatments were used further to intensities) shows that the signal-to-noise ratio for the 'as-prepared'
characterize the processes that occur during the oxygen turnover in sample is too low to make more or less definite conclusions about the
such idealized conditions. presence of the shake-up satellite in its spectrum. In spite of that, in the
case of the thermally-treated sample, this component in the spectrum
3.2. Surface composition and state of ions (XPS data) can be distinguished with a greater degree of certainty.
Also, the presence of carbon (C1 s line) was detected in form of two
The following characteristic lines in the photoelectron spectra were peaks at 284.8 and 288.2 eV. The former is well defined and obviously
analyzed: Si 2p, O 1 s, Na 1s, W 4f, and Mn 2p3/2. corresponds to the adventitious carbon. The latter peak is ca. 15-fold
The position, shape, and intensity of the Si 2p line remained vir- less intense and can be attributed to the presence of some carbonate
tually unchanged after the annealing in vacuum, whereas other lines species (most probably in a form of Na2CO3). The nature and behavior
underwent significant changes described below. of carbon-containing species are not further analyzed here in more
detail.
3.2.1. O 1s line All in all, the main conclusion from our XPS measurement is as
In the 'as-prepared' state (see Fig. 3a) the O 1s line spectrum consists follows: the desorption of the weakly-bonded reactive oxygen during
of two components. The more intense one (with high electron binding the vacuum annealing of the sample at 800 °C [19,20] is accompanied
energy 532.5 eV) is attributed to oxygen in SiO2, whereas the low-en- by a significant enrichment of the NaWMn/SiO2 oxide surface with
ergy one (530.3 eV) is assigned to the oxygen ions associated with supported components. The possible chemical nature of this phenom-
transition metals (W and Mn) [33,34]. enon was revealed in our further SEM/EDX measurements.

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M. Sinev et al. Catalysis Today 333 (2019) 36–46

Fig. 3. X-ray photoelectron spectra of the 'as-prepared' (curves 1) and vacuum-annealed (curves 2) NaWMn/SiO2 samples; (a) – O 1 s line; (b) – W 4f line; (c) – Mn 2p
line.

morphologies are represented by two distinct ones. According to the


EDX data, the one that has a brighter contrast contains Mn and W (see
Fig. 7); it can be associated with the MnWO4 phase identified by XRD
(see Fig. 2).
More detailed information on the chemical composition of the
particles with different morphologies can be obtained from the EDX
element mapping data (see Fig. 6).
The second matter differs substantially from all the others observed
in this work. According to the EDX spectra (see Fig. 8), it contains so-
dium and manganese. It is most likely amorphous, which is indicated by
its morphology: this matter seems to have a high adhesion to the silica
surface and forms a permanent network decorating the grain bound-
Fig. 4. Relative surface concentrations of elements in the 'as-prepared' and aries between the SiO2 bulbs. For greater certainty, hereafter it will be
vacuum-annealed NaWMn/SiO2 samples; numbers on the blue bars demon- conventionally called a "glue-like matter". Unlike SiO2, Na2WO4 and
strate the relative increase of the corresponding element-to-silicon ratio after MnWO4, the presence of such matter in NaWMn/SiO2 catalysts was not
the desorption of oxygen (For interpretation of the references to colour in this previously reported in the literature. It is worth noticing that MnWO4
figure legend, the reader is referred to the web version of this article). and the glue-like matter cover a substantial part of the free surface of
the SiO2 particles. This finding explains the XPS data that demonstrate a
3.3. SEM data significant increase in the Na:Si, W:Si, and Mn:Si ratios in the reduced
sample.
Microphotographs of the 'fresh' sample obtained by SEM with dif- The spectra in Fig. 8 also demonstrate that sodium is concentrated
ferent magnification are presented in Fig. 5 along with a wide EDX in the glue-like matter, whereas its concentration in the bare SiO2
spectrum that reveals the presence of Si, O, Na, W, and Mn in the particles is below the detection limit. Also, tungsten is not detected in
sample, while the SEM images demonstrate that there are particles of these two morphs.
different morphologies and chemical composition. The latter is evi- After re-oxidation, the general appearance of the sample virtually
denced by the difference in brightness since the heavier chemical ele- returns to the initial ('fresh') state. However, two important changes
ments give the brighter light contrasts of the particles observed in the must be noted. First, the fraction of small (sub-micron) Na2WO4 and
SEM images. Also, the EDX spectra indicate the presence of carbon in Mn2O3 particles substantially increases. Secondly, these small particles
this sample, as well as in the ones described below. As we mentioned of both chemical compositions are predominately concentrated on the
above, it can be attributed to both sodium carbonate and adventitious grain boundaries between the SiO2 bulbs and at their intersections (see
carbon. Figs. 7,8).
The almost ubiquitous presence of oxygen confirms that, as ex- Summarizing the experimental data, desorption of oxygen by an-
pected, all elements are present in the sample in an oxide form. SiO2 is nealing in vacuum or in an inert gas leads to a drastic change in the
represented by round-shape micron-size particles ('bulbs') connected to chemical state of the supported components.
a continuous network that forms a porous medium. Na and W are
mainly concentrated in loose micron-size agglomerates, although their 4. Discussion
presence in much smaller particles cannot be excluded. Manganese
oxide forms well-crystallized particles; their sizes range from sub-mi- The experimental data can be summarized as follows.
cron to micron. Interestingly, the Na- and W-containing structures (they
can be associated with the Na2WO4 phase observed in the XRD pat- 1 In the 'as-prepared' state and after quenching from the reaction
terns) fill the space between the Mn oxide crystals (Mn2O3, according to conditions at relatively low (∼50%) oxygen conversion the main
the XRD data), i.e., these two phases are in a tight contact. This means phases of the NaWMn/SiO2 catalyst are crystalline α-cristobalite
that the particles that belong to different phases (chemical compounds) (SiO2), sodium tungstate (Na2WO4), and manganese (3+) oxide
have extended surface contact, but not stay apart from each other or (Mn2O3). According to the SEM data, the latter two compounds are
only touch one another. in a tight contact.
Both the morphology of the particles and their chemical composi- 2 After quenching from the reaction mixture at high oxygen conver-
tion change dramatically after oxygen desorption (see Figs. 7,8). The sion and after oxygen desorption (annealing in vacuum or in a he-
well-crystallized structures totally disappear. The newly appeared lium flow) Na, W, and Mn form substances of a different phase

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M. Sinev et al. Catalysis Today 333 (2019) 36–46

Fig. 5. SEM images of the 'as-prepared' NaWMn/SiO2 sample with different magnification and its EDX spectrum.

composition. Their chemical nature was identified at room tem- presumably in the reduced Mn2+ state.
perature after oxygen desorption as crystalline manganese tungstate At the temperatures of oxygen desorption, the state of the glue-like
and a glue-like matter containing sodium and manganese, which is matter is likely molten: its distribution on the SiO2 surface indicates a
likely amorphous and covers the grain boundaries between the SiO2 wetting-like interaction. At low temperature, it retains high adhesion to
bulbs. Unfortunately, we could not determine the oxidation state of the SiO2 surface and, most likely, an amorphous structure.
manganese in this glue-like matter. The fraction of the SiO2 surface In the literature, there are no generally accepted concepts of me-
covered by the supported components significantly increases after thane activation sites in the NaWMn/SiO2 catalyst, the functions of its
oxygen desorption. components, and the nature of the reactive oxygen species. Here we are
3 Subsequent re-oxidation restores the initial chemical composition of mainly focused on the latter two aspects, particularly on the transition
the supported components, although the morphologies and locali- between different states of the active components during the release
zation of Na2WO4 and Mn2O3 change to some extent compared to and uptake of oxygen.
the initial ones. The fractions of small (sub-micron) particles of these We should emphasize once again that the presence of α-cristobalite,
compounds become more representative. Such small particles are sodium and manganese tungstates, and Mn2O3 phases in NaWMn/SiO2
localized predominately on the grain boundaries between the SiO2 catalysts prepared by different techniques and after different pre-
bulbs, i.e. in the same zones which are covered with the glue-like treatments ('as-prepared', after time-on-stream in the OCM reaction)
matter in the sample after oxygen desorption. has been repeatedly reported by many research groups (see, for in-
stance [27,29–38],). In several cases, the presence of some supported
Such observations suggest that the reversible release and uptake of components in a molten state has been discussed, mainly in the context
oxygen can be described by the following chemical equation: of a relatively low melting point of sodium tungstate (∼698 °C)
[33,34,37,38]. In [19] we mentioned that the oxygen desorption rate
Na2 WO4 + Mn2 O3 DMnWO4 + {Na2 MnOX } + (1.5–0.5X ) O2 (9)
sharply increases around this temperature, which is likely due to a
The formula in the braces {Na2MnOX} presents the assumed com- much higher molecular mobility in a liquid (molten) state.
position of the glue-like matter, which does not appear to have been Unlike many other researchers, the authors of [38,39] insist that Mn
described previously, but deserves much attention. Due to the facts that and W are not essential components for the selective OCM reaction.
small particles of Mn2O3 are found in the zone of the glue-like matter Based on the characterization data, including the in situ XRD, XPS, and
localization in the reduced state and that the amount of oxygen released laser-induced fluorescence (LIF) spectroscopy, in [38] it was concluded
in the course of desorption is equivalent to the Mn3+ content in the that the role of sodium consists in the formation of peroxide (Na2O2)
sample and its complete transfer to Mn2+ [19,20], one may conclude that further generates hydrogen peroxide; the subsequent decomposi-
that X = 2. In other words, manganese in the glue-like matter is present tion of the latter leads to the generation of free OH-radicals (detected

41
M. Sinev et al. Catalysis Today 333 (2019) 36–46

Fig. 6. SEM image and EDX element mapping of the 'as-prepared' sample.

using LIF spectroscopy in the O2-H2O-containing atmosphere at implicated as the OCM active sites.
900–950 °C), which are believed to be the main active species for H- A different role was attributed to the supported components in the
atom abstraction from methane molecule. The role of tungsten is as- earlier work [22]. Based on the data on the catalytic performance, bulk
signed to the capability of WO42− anions to immobilize Na in the form (XRD) and surface (XPS, 3He+-ion scattering) characterization, and
of tungstate and, therefore, to diminish its removal from the catalyst pulse reduction of various Na-, Mn-, and W-containing samples, it was
due to relatively low melting (∼320 °C) and boiling (1388 °C) points of concluded that the form of oxygen that abstracts a hydrogen atom from
NaOH. In spite of evident contradictions in such explanations (the ne- methane results from the activation of gaseous O2 by surface Mn and
cessity for sodium to be simultaneously in the oxide/hydroxide form to sodium is essential for preventing the complete oxidation of methane;
be able to produce peroxide, and in tungstate form for less volatility; the tungstate ions apper to impart the stability to the catalyst. The
the unclear role of Mn), the presence of a molten phase is acknowl- authors of [22] suggest the following scheme for the reversible oxygen
edged. Thermodynamic aspects of transitions between different sodium uptake
compounds will be discussed below.
MnOx + Na2WO4 DNa2O+MnWO4 +(1–0.5x)O2 (10)
On the contrary, most of the other research groups attribute the
redox behavior and the oxygen turnover during the catalytic reaction to which is similar to reaction (9) in the sense of the participation of
various W and/or Mn species. In contrast to [38], in [25] it was con- MnWO4 in the redox cycle. Nevertheless, the authors of [27] were not
cluded that sodium, as a chemical promoter, acts to disperse and sta- inclined to regard MnWO4 as the active species since this phase was not
bilize the key W surface species, possibly WO4, which are thought to be observed in the NaWMn/MgO catalyst, which is 'nearly identical' to the

Fig. 7. SEM images of NaWMn/SiO2 samples after different treatments: (a) – 'as-prepared'; (b) – after oxygen desorption; (c) – after re-oxidation.

42
M. Sinev et al. Catalysis Today 333 (2019) 36–46

Fig. 8. SEM image of NaWMnW/SiO2 sample after oxygen desorption and EDX spectra of the 'glue-like matter' and the bare part of the SiO2 bulb surface.

silica-supported one in terms of its catalytic performance. It was con- say how much these statments are internally consistent.
cluded that no single Mn phase is responsible for the high activity and The study described later in [26] led the group that included the
selectivity. Let us mention, however, that according to the experimental same authors as [23] to the following conclusions:
data presented in [22], the specific activity of silica supported catalyst,
in which MnWO4 is found, possesses about one order of magnitude • both Na-O-W and Na-O-Mn act as the active centers;
higher specific activity than the MgO-supported one, although in the • there is some sort of synergy of sodium, tungsten, and manganese
presence of both ones the same conversions and selectivities can be components;
achieved, but at different gas space velocities. Also, the activity of MgO- • the Na W O crystalline phase (not an amorphous feature as in
2 2 7
supported catalyst further decreased within 10 h on stream at 800 °C, [23]) is active for the OCM reaction.
whereas the silica-supported one was much more stable. Generally, in
[22] it was concluded that active centers consisting of a Mn-Na-O It is not clear how these conclusions correlate with each other and
species are responsible for the high activity and selectivity of the OCM with the results of [23].
reaction over these catalyst with no mentioning the role of phase The SEM/EDX along with some other ex situ characterization (XPS,
transitions, i.e., solid (crystalline and/or amorphous) ↔ liquid (melt). IR spectroscopy) [28] did not give much indication for the presence of
In [32] phase diagrams of the M(Li, Na, K, Rb, Cs)/W/Mn/SiO2 an amorphous phase, although based on the sum of the existing data the
systems were analyzed in detail and compared with existing data on authors expected the appearance of a melt in the course of the catalyst
their catalytic performance. It was concluded that in the most cataly- synthesis from the amorphous silica, sodium tungstate, and manganese
tically efficient compositions the alkali-metal tungstates are molten at nitrate, and both Mn and W were expected to be part of the melt. In the
typical OCM temperatures and oxygen partial pressures. The OCM 'as-prepared' catalyst three crystalline phases (α-cristobalite, Na2WO4,
process involves the mobile lattice oxygen of nonstoichiometric Mn2O3) were found, while after time-on-stream MnWO4 was detected
Mn2O3-δ (bixbyite), but at low oxygen partial pressures bixbyite indicating a partial reduction of the catalyst active coating. It was
transforms into manganosite (MnO), which then reacts with WO3 to concluded that the latter was stable during OCM, but seemed to have
yield hubnerite MnWO4, which is designated as catalytically inert. This melted and resolidified. No definite conclusion on the fate and/or the
assumes that all Mn-containing components in the system are solid role of MnWO4 was made, although it was mentioned also that the local
during the catalytic process and interact with alkali metal tungstates in coordination of the tetrahedral WO42− anion is different in two tung-
the molten state. No further details on the mechanism of the catalytic states (MnWO4 and Na2WO4). This may affect the efficiency of methane
reaction and/or the oxygen turnover are provided. activation, if the catalytic behavior is correlated to this anion.
Based on the ex-situ characterization (data obtained by XPS, EXAFS, The formation of MnWO4 phase in 'as-prepared' catalysts obtained
XANES, and IR spectroscopy) [23] it was concluded that the high ac- using different SiO2 supports received much more attention in [29].
tivity of the manganese-tungsten catalyst is due to the surface oxygen Nevertheless, no clear correlation between its initial concentration and
species, which are pre-activated from lattice oxygens to "the nearest catalytic performance was found. However, in situ XRD data (at 750 °C)
oxygens" by the surface in an amorphous state. This means that the showed that in the raction conditions a detected phase of active com-
main role in catalysis is assigned to the surface amorphous feature, but ponent was always MnWO4 formed from braunite (MnMn6SiO12) and
not to any of crystalline phase present in the system. It was also stated molten Na2WO4. The amount of manganese tungstate in the working
that the manganese species as a good oxygen-releaser is not as good as catalyst increased with time-on-stream, but, unfortunately, its role in
an oxygen-catcher, and only if either W- or Mn-tetrahedral centers the catalytic process was not further discussed.
necessary for the activation of methane and Mn-octahedral centers Let us mention, however, that manganese tungstate is the com-
(good at catching as well as releasing oxygen) are present on the surface pound in which two elements – Mn and W – are in the closest possible
simultaneously, a high efficiency in OCM can be achieved. It is hard to interaction and share the same oxygen ions. This means that if one

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M. Sinev et al. Catalysis Today 333 (2019) 36–46

considers W-O-Mn groups as active sites (see, for instance [23],), this eutectic (∼8 mol. % of Na2CO3) that melts at 286 °C. If both hydroxide
compound can be considered as a possible active phase. The Mn2+ ions and carbonate are present in the system, the fraction of the molten
present in they can serve as the centers for O2 molecule activation. phase should increase as the H2O : CO2 ratio insceases in the reaction
According to the data obtained in this work, even in the absence of mixture at temperatures below ∼850 °C.
methane, MnWO4 undoubtedly participates in the redox cycle. It ac- The data of Table 1 also indicate that the formation of sodium
commodates tungsten and, at least in part, manganese in the reduced peroxide in the conditions of the OCM process is thermodynamically
state; it should be able to undergo re-oxidation, which means that its improbable, especially at high oxygen conversions and high con-
reactivity is essential and sufficient for the overall reaction turnover, centrations of water and CO2, i.e., in the steady-state OCM reaction
even if it does not activate methane directly. conditions, the formation of Na2O2 is suppressed. Also, in the presence
Alternatively, one may suppose that the whole redox cycle proceeds of CO2 transformation of sodium tungstate to Na2CO3 and WO3 is more
in the melt that contains simultaneously Na+, Mn3+/Mn2+, and W6+ probable (ΔG ∼ 0).
in the form of WO42−, as well as other oxygen-containing anions. In addition to the effect of temperature and chemical composition of
Indeed, at least one of the substances initially present in the system, the reaction mixture on the phase state of the supported components,
namely sodium tungstate, is definitely liquid at the temperatures of their influence on the catalyst redox state should be analyzed as a factor
both the main oxygen desorption and the OCM reaction. As we noted that causes the results of both in situ and ex-situ measurements of the
above, the glue-like matter that is present in the reduced sample most catalyst composition. According to the redox (Mars-van Krevelen) ki-
likely forms a surface molten phase too. The morphology of MnWO4 netic model, the rate of reaction is proportional to the oxidation degree
(see Fig. 7b) allows one to suppose that it precipitates from some of the catalyst active sites Θ (see Eq. (1a)). Since in the case of the OCM
general melt due to its segregation, either during the desorption of kinetics over the NaWMn/SiO2 catalyst m = n = 1 [17], we can re-
oxygen (which is consistent with data of [29]), or in the course of write Eq. (1)b as follows:
cooling, while the remaining part of the molten phase congeals as the
WOCM = Θ kred PCH 4 (2)
glue-like matter containing Na and Mn.
Figs. 5 and 7a, c show that in the oxidized state at room temperature and
Na2WO4 and Mn2O3 phases are in a tight contact. This strongly suggests −1
k
that at temperatures higher than the Na2WO4 melting point (698 °C) Θ = ⎛1 + α red ⎞
⎜ ⎟

Mn2O3 is in a direct contact with the melt and any interactions between ⎝ kox ⎠ (3)
them, including cation exchange and oxygen evolution/consumption, where α = PCH4/PO2. This parameter determines the redox potential of
can easily proceed. Unfortunately, any further reasoning is speculative the OCM reaction mixture in the steady-state conditions. The following
because we do not possess any data on the solubility of solid Mn2O3 in expressions for kinetic constants
molten Na2WO4, as well as on the miscibility of liquid phases which can
appear in the system in oxidized, reduced, and intermediate states. kred = 2.5 × 109exp[–23150/T],s-1,
Anyhow, the newly obtained data evidence that all three elements –
Na, W, and Mn – are involved into the chemical and structural changes k ox = 1.7 × 101exp[–24160/T],s-1 (1)
during the oxygen turnover. This well correlates with our previous were obtained from our experimental data for the same catalyst
observation [19], according to which a significant amount of oxygen [17]. The effects of α and temperature on the Θ value according to Eq.
can be reversibly released (desorbed) only if all three components are (3) are shown in Fig. 9. In typical initial OCM gas mixtures, the me-
present in the catalyst simultaneously. Neither two-component (Na-W, thane concentration is 2–10 times higher than that of oxygen, i.e.
Na-Mn, Mn-W), nor one-component systems do not possess such re- α = 2–10. The solid lines (1)-(3) in Fig. 9 are drawn for this range of α.
active oxygen. And namely this 'weakly-bonded' and 'short-lived' Due to the large excess of methane, the mixture is depleted in oxygen in
oxygen is highly active while reacting with methane to produce the the course of reaction, and α can reach very high values up to 103 and
OCM products (ethane and ethylene) [19]. even more. The dashed lines (4)-(6) in Fig. 9 demonstrate the tendency
Let us, however, consider what can happen in the steady-state OCM of the Θ change with increasing oxygen conversion. Generally, while
reaction conditions when methane, oxygen, and reaction products – oxygen conversion is low, the degree of catalyst oxidation is high in the
including water and CO2 – are present simultaneously. We certainly can whole range of typical OCM temperatures. The Θ value drastically de-
assume that in addition to the substances which occur in the conditions creases with increasing oxygen conversion. In particular, while
experimentally studied in this work, when oxygen is the only reactive quenching the samples from the reaction mixture at relatively low (∼
gas present in the system, the components of the catalyst can form
hydroxides, carbonates, and probably peroxides [38]. Among them,
sodium hydroxide and carbonate are thermodynamically the most
stable (see Table 1). Also, these two compounds have relatively low
melting points (∼320 °C for NaOH and 852 °C for Na2CO3) and form an

Table 1
Thermodynamic parameters of selected reactions of sodium compounds.
No. Reaction ΔH°298, kcal/ ΔG°298, kcal/mole
mole

1. Na2O(s) + H2O ⇆ 2 NaOH(s) −43.3 −33.9


2. Na2O(s) + CO2 ⇆ Na2CO3(s) −72.95 −62.3
3. Na2CO3(s) + H2O ⇆ 2 NaOH(s) + +29.65 +28.4
CO2
4. Na2O(s) + 1/2 O2 ⇆ Na2O2(s) −19.2 −13.5
5. Na2WO4(s) + H2O ⇆ 2 NaOH(s) + +22.7 +31.75
WO3(s) Fig. 9. Degree of the catalyst active sites oxidation as a function of temperature
6. Na2WO4(s) + CO2 ⇆ Na2CO3(s) + −6.95 +3.35
at α = 2 (curve 1), 4 (curve 2), 10 (curve 3), 20 (curve 4), 50 (curve 5), 100
WO3(s)
(curve 6), and 500 (curve 7).

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M. Sinev et al. Catalysis Today 333 (2019) 36–46

50%) and high (> 95%) degree of oxygen conversion, the corre- phase(s) (melt), in which all chemical and mass-transfer processes are
sponding α values were estimated as ∼10 and > 100. According to the fast. We may agree with the conclusion made in [27] that sodium is
data of Fig. 1 in these two states the Θ values are ∼0.73 and < 0.2, essential for preventing the complete oxidation of methane, but in the
respectively. This is in a good agreement with the XRD data presented sense that its liquid compounds block the surface of Mn2O3 particles,
in Fig. 2. thus hindering their direct interaction with gaseous species.
If the reaction proceeds in a plug-flow reactor with elongated cat- The presence of manganese (2+) at reaction temperatures in two
alyst bed, the degree of the catalyst oxidation varies along its axis, and different phases, namely MnWO4 and Na-Mn-O melt (supposedly close
after unloading the reactor, the results of the catalyst characterization to Na2MnO2 by stoichimetry), can explain the linear decrease of the
may be misleading. heat of re-oxidation observed in [20]: even if the final oxidized state is
We should mention here that there is a discrepancy in the inter- the same (Mn2O3), the heat evolved during re-oxidation depends on the
pretations of pulse experiment results in [19] and [22]. Based on the enthalpy of the initial state and on the formal stoichiometry of re-oxi-
difference in the rates of the catalyst reduction with methane and the dation:
steady-state OCM reaction, J.H. Lunsford and co-workers concluded
MnWO4 + 1/2O2 ®Mn2 O3 + 2{WO3 } (11)
that the oxygen that somehow belongs to the phases of the catalyst
active coating ("lattice oxygen in the bulk of the catalyst") does not Na2MnO2+O2 + 2{WO3 } ®Mn2 O3 + 2 Na2WO4 (12)
participate in the catalytic process. The active center is believed to be a
transient state that exists only in the presence of gas-phase O2, and none where {WO3} is tungsten oxide either in the free crystalline state (m.p.
of the crystalline present in the catalyst is directly associated with the 1470 °C), or dissolved in the melt, which is present on the surface.
catalytic performance: these phases may be indirectly involved by in- The sum of reactions (11) and (12), obviously, gives the reverse
fluencing the concentration and oxidation state of Mn on the surface reaction (9) (supposing that X = 2). But if these two reactions proceed
[22]. sequentially, the heat evolution measured during the oxidation in the
However, the kinetic analysis performed in [19] showed that the pulse regime would be a function of the amount of previously con-
lifetime of the 'weakly-bonded' oxygen present in the oxidized catalyst sumed oxygen or, in other terms, the pulse number.
is much longer than the characteristic time of the catalytic OCM reac- Three important comments regarding our experimental observa-
tion in the steady-state conditions. And it is for this reason that the rate tions should be added. The first one is associated with the XPS signal
of the steady-state OCM reaction can be satisfactorily described by Eqs. that was attributed to the reduced W4+ state. Although its relative in-
1–3. tensity is low, it indicates anyway that there is some non-uniformity of
According to the experimental data obtained in this work, we con- the state of tungsten in the sample after desorption of oxygen.
clude that the phase composition of the sample changes drastically after Unfortunately, at this stage we cannot assign this signal to any parti-
desorption of oxygen which is associated with the Mn3+ → Mn2+ redox cular compound or phase observed by XRD and/or SEM.
transition. The phases that are detected in the catalyst in oxidized ('as- The second comment concerns the chemical purity of the SiO2 (α-
prepared' and 're-oxidized') and reduced (after oxygen desorption) cristobalite) phase bulk and surface. Although its doping with sup-
states at room temperature, as well as those anticipated at reaction ported metal components is extensively discussed in the literature, in
(oxygen desorption / re-oxidation and steady-state catalytic OCM) our experiments we could not find any indications of this. One may
temperatures are given in Table 2. A molten state of the sodium con- assume that even if such doping takes place, its contribution to the
taining components in the reaction conditions is unquestionable, al- phenomena studied in this work, namely reversible oxygen evolution
though we may doubt concerning the presence of tungsten in the melt. and uptake, is negligible, and the predominate amount of this oxygen
Likewise, the miscibility of liquid phases cannot be estimated based on ('weakly-bonded') is associated with that part of the deposited compo-
the available information. As a result, we may conclude that the nents that form clearly observed phases. As to the centers of methane
NaWMn/SiO2 catalyst is highly active due to the presence of liquid molecule activation, this very important issue should be discussed se-
parately and based on additional experimental and theoretical argu-
Table 2 ments.
Phase composition of the NaWMn/SiO2 catalyst at different temperatures in The last, but not least important point concerns the glue-like matter,
oxidized and reduced states, and in steady-state conditions (catalytic OCM re- which seems to play a key role in the turnover of oxygen. As we already
action). noted, we could not find in the literature any mention of its observa-
State of the catalyst* Temperature
tion. This can be caused by one important difference in the experi-
mental procedures, namely in the preparation of samples for the SEM/
25 °C (observed) > 700 °C (anticipated) EDX analysis. Unlike other authors (see, for instance [28],) negative
(room temperature) (oxygen desorption, steady-state effects of the sample charging were eliminated by varying the working
OCM)
parameters, as described in Experimental section. This avoided the use
oxidized Na2WO4 Na2WO4 (molten); of carbon coating to improve the sample conductivity and to prevent its
(crystalline); Mn2O3 (crystalline); charging. Such coating can decorate the sample and hinder the ob-
Mn2O3 (crystalline); servation of some important features. As for the other observations,
reduced MnWO4 {Na-Mn2+-O + W(?)} (molten);
they are similar for the "as-prepared" samples in this work and in [28],
(after oxygen (crystalline); MnWO4 (crystalline?)
desorption) glue-like matter as well as for samples after desorption of oxygen (this work) and after
(amorphous) the time-on-stream in [28].
steady-state OCM Na2WO4 (molten);
reaction** {Na-Mn2+-Mn3+-O + W(?)}
(molten);
5. Summary
MnWO4 (crystalline?);
Mn2O3 (crystalline); Oxygen desorption from three-component supported NaWMn/SiO2
Na2CO3 (crystalline below catalyst at 800–900 °C in vacuum or in inert gas leads to a drastic
∼850 °C);
change of its phase composition. Crystalline Na2WO4 and Mn2O3 phases
NaOH-Na2CO3 eutectic (molten)
disappear, and newly-formed compounds solidify in the form of crys-
* α-cristobalite phase is not shown, it is present in all states. talline MnWO4 and the glue-like matter. The latter contains sodium and
** fractions of different phases vary depending on the steady-state methane- most likely manganese in the (2+) oxidation state. Its localization on
to-oxygen ratio (see Fig. 8 and corresponding comments in the text). the grain boundaries of the SiO2 (α-cristobalite) bulbs and morphology

45
M. Sinev et al. Catalysis Today 333 (2019) 36–46

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