Rare Met.

(2014) 33(2):230–238 RARE METALS

DOI 10.1007/s12598-013-0173-3 www.editorialmanager.com/rmet

Selective oxidation of methane and carbon deposition over

Fe2O3/Ce12xZrxO2 oxides
Xiu-Li Sang, Kong-Zhai Li*, Hua Wang,
Yong-Gang Wei

Received: 19 August 2013 / Revised: 12 October 2013 / Accepted: 20 November 2013 / Published online: 5 December 2013
Ó The Nonferrous Metals Society of China and Springer-Verlag Berlin Heidelberg 2013

Abstract A series of Fe2O3/Al2O3, Fe2O3/CeO2, Ce0.7 filament, resulting in a loose contact between the carbon
Zr0.3O2, and Fe2O3/Ce1-xZrxO2 (x = 0.1–0.4) oxides was filament and the catalyst. This results in abundant exposed
prepared and their physicochemical features were investi- active sites for catalyzing carbon oxidation, strongly
gated by X-ray diffraction (XRD), transmission electron improving the oxidation rate of the carbon deposition over
microscope (TEM), and H2-temperature-programmed this sample. In addition, the Fe2O3/Ce0.7Zr0.3O2 also rep-
reduction (H2-TPR) techniques. The gas–solid reactions resents much higher selectivity (ca. 97 %) for the conver-
between these oxides and methane for syngas generation as sion of carbon to CO than the Fe2O3/CeO2 sample, which
well as the catalytic performance for selective oxidation of can be attributed to the higher concentration of reduced
carbon deposition in O2-enriched atmosphere were inves- cerium sites on this sample. The increase of the Zr content
tigated in detail. The results show that the samples with the in the Fe2O3/Ce1-xZrxO2 samples could improve the
presence of Fe2O3 show much higher activity for methane reactivity of the materials for methane oxidation, but it also
oxidation compared with the Ce0.7Zr0.3O2 solid solution, reduces the selectivity for CO formation.
while the CeO2-contained samples represent higher CO
selectively in methane oxidation than the Fe2O3/Al2O3 Keywords Methane; Carbon deposition; Gas–solid
sample. This suggests that the iron species should be the reaction; Selective oxidation of carbon;
active sites for methane activation, and the cerium oxides Fe2O3/Ce1-xZrxO2 catalysts
provide the oxygen source for the selective oxidation of the
activated methane to syngas during the reaction between
methane and Fe2O3/Ce0.7Zr0.3O2. For the oxidation process 1 Introduction
of the carbon deposition, the CeO2-containing samples
show much higher CO selectivity than the Fe2O3/Al2O3 The direct conversion of methane to syngas (a mixture of
sample, which indicates that the cerium species should play CO and H2) using the redox property of solid oxides is a
a very important role in catalyzing the carbon selective novel method for syngas generation [1, 2]. This process can
oxidation to CO. The presence of the Ce–Zr–O solid be achieved in two interconnected reactors. The methane is
solution could induce the growth direction of the carbon oxidized by solid oxides (oxygen carrier) to carbon mon-
oxide and hydrogen in the fuel reactor, and then the
reduced oxygen carriers are transferred to the regeneration
X.-L. Sang reactor and re-oxidized by oxygen. The oxygen carrier is
Quality Development Institute, Kunming University of Science
recycled between both reactors with the successive pro-
and Technology, Kunming 650093, China
duction of syngas. In this process, separating the methane
K.-Z. Li*, H. Wang, Y.-G. Wei side from the gaseous oxidant could avoid the risk of
Engineering Research Center of Metallurgical Energy explosion and the dilution of product gas with nitrogen [3,
Conservation and Emission Reduction, Ministry of Education,
4]. However, one of the most serious problems of this
Kunming University of Science and Technology,
Kunming 650093, China method is the formation of a great amount of carbon
e-mail: [email protected] deposition when most of the lattice oxygen in the oxygen

123
Selective oxidation of methane and carbon deposition over Fe2O3/Ce1-xZrxO2 oxides 231

carrier were consumed during the gas–solid reaction. Since 65 cm3 of slurry was transferred to 100 cm3 Teflon–lined
the amount of the lattice oxygen in the oxygen carrier is stainless steel autoclaves and reacted at 220 °C for 48 h.
very limited, a short reaction time is necessary for avoiding After cooling, the samples were washed with distilled
the formation of carbon deposition. This makes the method water and ethanol for three times before air drying at
uneconomical because of relative high operation cost 110 °C for 12 h. Then, the samples were calcinated at
caused by the short period of redox cycle. 800 °C for 6 h. For the Fe2O3/Al2O3 and Fe2O3/CeO2
In this case, considerable attention has been focused on samples, both the Fe/Al and Fe/Ce molar ratios were 3:7.
the gasification of carbon deposition to CO, which can be The Fe/(Ce?Zr) molar ratios in all the Fe2O3/Ce1-xZrxO2
combined with the step of methane decomposition (H2 samples were also maintained at 3:7.
generation) to produce syngas. It was reported that
deposited carbons could be gasified with steam or CO2 to 2.2 Material characterization
syngas or CO [5–9]. Unfortunately, the carbon deposition
cannot be completely removed by steam or CO2 [5, 6, 9], The powders X-ray diffraction (XRD) experiments were
and the removal rate of carbon is very low [9]. As a result, performed on a Japan Science D/max-R diffractometer
a gradual decrease in the catalytic activity for the methane using Cu Ka radiation (k = 0.15406 nm). The X-ray tube
decomposition was observed during the cycles [5, 6, 9]. was operated at 40 kV and 40 mA. The X-ray diffracto-
It is well known that the carbon deposition could be gram was recorded at 0.01° intervals in the range of
removed efficiently by O2, but the major production was 10° B 2h B 80° with 3 s count accumulation per step. The
general carbon dioxide rather than the desirable carbon identification of the phase was made with the help of the
monoxide [9, 10]. Fathi et al. [11] observed that the carbon JCPDS cards (Joint Committee on Powder Diffraction
formed on the Pt/CeO2/c-Al2O3 catalysts in the process of Standards).
partial oxidation of methane could be oxidized selectively Temperature–programmed reduction (TPR) experiments
(almost 100 %) to carbon monoxide at 700 °C. It also were performed on a TPR Win v 1.50 (produced by
showed that a large amount of CO was produced during Quantanchrome Instruments Co.) under a 10 % H2/He
pulsing with oxygen after repetitious pulses of methane mixture (75 ml
min-1) flow using 100 mg catalysts at a
over LaFeO3 catalyst (carbon deposition formed during the heating rate of 10 °C
min-1.
methane pulses), while no CO2 was detected [12]. Previ- The microstructures and morphologies were investi-
ously, we reported that carbon deposition could be selec- gated using a JEOL JEM-2100(UHR) transmission electron
tively oxidized to CO with little CO2 evolution by oxygen microscope (TEM) at 200 keV.
over the CeO2–Fe2O3 catalysts [13, 14]. However, detailed
information on the functions of different species in the 2.3 Reactions
catalyst system is still missing.
In the present work, comparative studies were per- The reactions with methane: the gas–solid reactions were
formed on the reactivity of Fe2O3/Al2O3, Fe2O3/CeO2, carried out in a quartz fixed bed reactor (14 mm inside
Ce0.7Zr0.3O2, and Fe2O3/Ce1-xZrxO2 (x = 0.1–0.4) oxides, diameter) under atmospheric pressure. Prior to the reac-
which own different states of ceria and iron oxides, for tions, the samples (1 g) were heated in air at 300 °C for
methane selective oxidation to syngas via gas–solid reac- 1 h, and then pure N2 flowed through the reactor for
tion. The oxidation of carbon deposition to CO by oxygen 15 min to remove the contamination on the sample surface.
over such samples was also investigated. The roles of the The temperature-programmed reactions between methane
ceria-based solid solution and iron species in methane (10 vol% CH4/N2 at a flow rate of 20 ml
min-1) and
conversion and carbon oxidation were discussed in detail. oxygen carriers were performed from 300 to 900 °C with a
heating rate of 10 °C
min-1, and the isothermal reactions
(with a sample flow rate of CH4/N2) were carried out at
2 Experimental 700 °C.
Carbon oxidation reactions: to obtain carbon deposition,
2.1 Materials preparation all the oxygen carriers (catalysts, 1 g) were treated in a
stream of methane (pure methane at a flow rate of
The required amounts of Ce(NO3)3
6H2O, Al(NO3)3
9H2O, 10 ml
min-1) at 700 °C for 120 min. The re-oxidation of
Zr(NO3)4
5H2O, and/or Fe(NO3)3
9H2O were dissolved in the carbon deposition on the reduced catalyst was per-
deionized water and well mixed with the total concentra- formed at 700 °C using 10 vol% O2/N2 at a flow rate of
tion of cation at 0.25 mol
L-1. A brown slurry was pre- 200 ml
min-1. These sequences were separated by a purge
cipitated by gradually dripping in an ammonia solution of pure N2 (60 ml
min-1) for 10 min to avoid the mixing
while maintaining the pH at ca. 10 with stirring. Then, of methane and oxygen. The amount of carbon deposition

Rare Met. (2014) 33(2):230–238 123

232 X.-L. Sang et al.

Fig. 1 XRD patterns of prepared samples Fig. 2 H2-TPR profiles of prepared samples

was quantified by combustion gas chromatography. A

nondispersive IR (NDIR) gas analyzer (C600, Shanghai which is lower than either Ce0.7Zr0.3O2 or Fe2O3/CeO2
Baoying technology Co.) was used to monitor the con- samples. In addition, an obvious shift to higher 2h position
centration of CO and CO2 continuously in the effluent gas is observed for the Fe2O3/Ce0.7Zr0.3O2 compared with the
from both the methane reactions and the carbon oxidation. Fe2O3/CeO2 sample. This suggests Fe2O3/Ce0.7Zr0.3O2
In addition, an Agilent 7890 gas chromatograph equipped sample contains both Ce–Fe–O and Ce–Zr–O solid solu-
with a TCD detector and two capillary columns (HP-PLOT tions. Compared with the Fe2O3/CeO2 sample, the char-
5A and HP-PLOT-Q) was also used for the qualitative acteristic peaks of Fe2O3 on the Fe2O3/Ce0.7Zr0.3O2 sample
analyses of product components. are much broader, suggesting smaller particle of free
Fe2O3. It is also noted that the characteristic peaks toward
CeO2 for the Fe2O3/Ce0.7Zr0.3O2 sample are much stronger
3 Results and discussion and sharper than that toward the Ce0.7Zr0.3O2 sample. This
indicates that the presence of Fe2O3 may improve the
3.1 Material characterization growth of the Ce0.7Zr0.3O2 solid solution particles.
The H2-TPR profiles of the prepared Fe2O3/Al2O3,
Figure 1 shows the XRD patterns of the Fe2O3/Al2O3, Ce0.7Zr0.3O2, Fe2O3/Ce0.7Zr0.3O2, and Fe2O3/CeO2 sam-
Ce0.7Zr0.3O2, Fe2O3/Ce0.7Zr0.3O2, and Fe2O3/CeO2 sam- ples are shown in Fig. 2. The Fe2O3/Al2O3 sample shows a
ples. It can be seen that Al2O3 feature is not observed main reduction peak at ca. 590 °C and a weak broad band
clearly in the Fe2O3/Al2O3 sample, suggesting that this over 600 °C, associating with the stepwise reduction of
phase displays poor crystallinity or small crystal size. The Fe2O3 through Fe3O4/FeO to Fe [16]. The Ce0.7Zr0.3O2
characteristic peaks toward Fe2O3 on this sample are also sample features two peaks at ca. 625 °C (major peak) and
very weak and broad, which indicates that Fe2O3 particles over 900 °C (minor peak), which can be associated with
are well dispersed on the Al2O3 support. For the the reduction of the surface and bulk Ce4?, respectively
Ce0.7Zr0.3O2 sample, only the characteristic reflections of [17].
cubic CeO2 could be detected. A contraction of the cell For the Fe2O3/Ce0.7Zr0.3O2 and Fe2O3/CeO2 samples,
parameter compared with the pure CeO2 (0.5381 nm for they represent similar profiles with four reduction peaks (a,
Ce0.7Zr0.3O2 vs 0.5411 nm for pure CeO2) is also observed. b, c, and d). Since both the two sample contains free Fe2O3
This indicates that all the Zr4? are incorporated into the particles and CeO2-based solid solution, it is suggested that
lattice of CeO2 to form a CeO2–ZrO2 solid solution [15]. the first reduction peak (a peak) is related to the free Fe2O3
Both CeO2 and a-Fe2O3 characteristic peaks appear in the reduction to magnetite; the second and third peaks (b and c
Fe2O3/Ce0.7Zr0.3O2 and Fe2O3/CeO2 samples. The lattice peaks) can be attributed to the reduction of uppermost
constant of the cubic cell of ceria in Fe2O3/CeO2 sample is layers of Ce4? and the simultaneous reduction of Fe2? to
found to be equal to 0.5395 nm which is a little smaller Fe; and the fourth peak (d peak) is unambiguously assigned
than that of pure CeO2 (0.5411 nm). This suggests that to the reduction of bulk CeO2 which only occurs at high
only a small part of Fe3? is incorporated into the ceria temperatures [18–21]. It should be stressed that a new
lattice to form solid solutions and the rest are left on the reduction peak (e) at ca. 370 °C weas observed over Fe2O3/
surface of the iron oxide. On the other hand, the lattice Ce0.7Zr0.3O2 sample, indicating relatively high concentra-
constant of ceria in Fe2O3/Ce0.7Zr0.3O2 sample is 0.5372, tion of surface adsorbed oxygen.

123 Rare Met. (2014) 33(2):230–238

Selective oxidation of methane and carbon deposition over Fe2O3/Ce1-xZrxO2 oxides 233

Fig. 3 Temperature programmed surface reaction between methane

and different samples Fig. 4 Isothermal reaction between methane and different samples at
700 °C
3.2 Methane oxidation reactions
CeO2–Fe2O3 oxygen carriers at high temperatures
Figure 3 shows the concentrations of CO and CO2 during (C800 °C) were studied [20, 25–27]. However, the reac-
the temperature programmed reactions between methane tivity of the oxygen carriers at relative lower temperatures
and different oxygen carriers. It is clear that the reaction for (e.g., 700 °C, which is the critical temperature for CO
each sample is very inefficient at low temperatures but the formation) is still missing. Therefore, the isothermal reac-
reaction rate increases quickly when the temperature rises tions of methane and different oxygen carriers at 700 °C
over 700 °C. The oxidation of methane by gas–solid were investigated in the present work, as shown in Fig. 4.
reaction in the absence of gaseous oxygen is closely related The reaction behaviors of the oxygen carriers at 700 °C
to the activity of oxygen species in the oxygen carriers. It is (Fig. 4) are totally different with the temperature pro-
reported that the most reactive oxygen is mainly removed grammed reactions. It is observed that the isothermal
at low temperatures giving deep oxidation products, while reaction between methane and Fe2O3/Al2O3 goes very
CO is mainly produced at higher temperatures [12, 22–24]. quickly and mainly produces CO2. For the CeO2-contained
This observation is proved in this work. CO2 with rela- samples (Ce0.7Zr0.3O2, Fe2O3/Ce0.7Zr0.3O2, and Fe2O3/
tively high concentrations are observed at the low-tem- CeO2), CO2 concentration is relative high at the early stage
perature region, and CO is detected as the main product at of the reactions but decreases sharply later, and then the
high temperatures. It should be noted that the CO con- CO increases to be the main product. Among the three
centration for the Fe2O3/Ce0.7Zr0.3O2 sample increases CeO2-contained samples, the reactivity of Ce0.7Zr0.3O2 is
quickly and reaches to the top at ca. 800 °C, which is much much weaker than the other two samples.
lower than that toward the other samples. The H2 evolution It was reported that the oxygen provided by the reduc-
is found to be in accordance with CO by GC measurements tion from Fe2O3 to Fe3O4 mainly participates in the com-
(not shown). This indicates that Fe2O3/Ce0.7Zr0.3O2 could plete oxidation of methane, and then the deeper lattice
convert methane to syngas at relatively lower temperatures oxygen could selectively convert methane to CO and H2
than other samples. [28, 29]. The high CO2 selectivity of the products for the
Isothermal reactions were performed to further investi- Fe2O3/Al2O3 samples indicates that Fe2O3 can only be
gate the reactivity of the prepared samples. In our previous reduced to Fe3O4 at 700 °C by methane, resulting in the
works, the isothermal reactions between methane and formation of the CO2. The formation of the CO2 at the

Rare Met. (2014) 33(2):230–238 123

234 X.-L. Sang et al.

Table 1 Amount of carbon deposition after methane decomposition

and average selectivity of CO during carbon oxidation stage for dif-
ferent samples
Samples Amount of carbon Average selectivity
deposition/(mg
g-1) of CO/%

Fe2O3/Al2O3 42.3 69.7

Ce0.7Zr0.3O2 14.2 95.8
Fe2O3/Ce0.7Zr0.3O2 29.6 97.2
Fe2O3/CeO2 39.5 86.6

early stage of the reactions toward the Fe2O3/Ce0.7Zr0.3O2

and Fe2O3/CeO2 can also be partially ascribed to the
reduction of the superficial layer of free Fe2O3 particles. It
was reported that the lattice oxygen of CeO2 could selec-
tively convert methane to CO and H2 only after the most
reactive oxygen (surface absorbed oxygen) were removed
[3, 11, 30, 31]. In this case, the CO2 formed over the
Ce0.7Zr0.3O2 sample should be attributed to the consump-
tion of the surface absorbed oxygen on this material.
For the reactions between methane and CeO2-based oxides,
it is proposed that the presence of promoters (e.g., Pt and Rh)
could drastically enhance the conversion of methane to syngas
due to their function for methane activation [11]. Our previous
study showed that the surface free iron oxides on CeO2 could Fig. 5 Carbon oxidation with oxygen over different samples at
not only activate methane but also provide the pathways for 700 °C
oxygen diffusion from the CeO2 lattice when it was reduced
during the reaction between methane CeO2–Fe2O3 mixed
oxides [26]. In this case, the low activity of Ce0.7Zr0.3O2 for of 10 ml
min-1) at 700 °C for 120 min. The amount of
methane oxidation in Fig. 4 may be attributed to the absence formed carbon deposition, as shown in Table 1, was
of active species for methane activation. On the other hand, the quantified by the combustion gas chromatography method.
relatively high activity of the Fe2O3/Ce0.7Zr0.3O2 and Fe2O3/ It can be seen that the amount of carbon on reduced
CeO2 samples must be related with the presence of the surface Ce0.7Zr0.3O2 sample is very low. By contrast, the Fe2O3-
iron species, because the supported metallic iron is active for contained samples, especially the Fe2O3/Al2O3 sample,
methane conversion [20]. The reduction process of the surface show much higher carbon content. This can be attributed to
iron oxides, which must create active species (reduced iron the catalytic action of supported iron species for methane
species) for methane oxidation, leads to the increase of the CO decomposition [8, 32]. Since the Fe2O3 particles on the
produced during the reaction. Fe2O3/Al2O3 sample own smaller size and higher disper-
The XRD data in Fig. 1 shows that Fe2O3 particles on sion than that on the other Fe2O3-contained samples, which
the Fe2O3/Ce0.7Zr0.3O2 sample are much smaller than that may result in relative higher activity of the Fe2O3/Al2O3
on the Fe2O3/CeO2 sample, which will certainly improve for methane decomposition, obtaining more carbon
the activity of Fe2O3/Ce0.7Zr0.3O2 sample for methane deposition.
oxidation. In addition, it is generally accepted that the The oxidation process of the carbon deposition on the
CeO2–ZrO2 solid solution owns higher mobility of lattice reduced oxygen carriers are represented in Fig. 5. It can be
oxygen than pure CeO2. Therefore, the higher activity of seen that it produced significant quantities of CO at the
Fe2O3/Ce0.7Zr0.3O2 for methane oxidation than the Fe2O3/ preliminary stage for all the samples, and only a few of
CeO2 sample can be attributed to the coexistence of smaller CO2 could be detected in the end of the oxidation process.
Fe2O3 particles and Ce0.7Zr0.3O2 solid solution. The average selectivity of CO (i.e., CO/(CO?CO2)) in the
oxidation products is shown in Table 1. It can be seen that
3.3 Selective oxidation of carbon deposition the CeO2-contained samples (Ce0.7Zr0.3O2, Fe2O3/CeO2,
and Fe2O3/Ce0.7Zr0.3O2) show much higher CO selectivity
To obtain carbon deposition, all the oxygen carriers were than the Fe2O3/Al2O3 sample. The Fe2O3/Ce0.7Zr0.3O2
treated in a stream of methane (pure methane at a flow rate represents the highest CO selectivity (97.2 %) among the

123 Rare Met. (2014) 33(2):230–238

Selective oxidation of methane and carbon deposition over Fe2O3/Ce1-xZrxO2 oxides 235

four samples. These indicate that the cerium oxides likely to be present on the iron surface. It can be speculated
(including Ce–Zr–O solid solution) should play an impor- that most of the iron sites on the Fe2O3/Al2O3 sample may
tant role in the selective oxidation of carbon deposition to be covered by the carbon deposition after a long time of
CO. methane decomposition. Our earlier studies show that the
It is noted that the dynamic oxidation behaviors of high oxidation rate of the carbon deposition can be
carbon deposition on the Fe2O3/Al2O3 sample are totally obtained in the presence of reduced species (metal particles
different with that toward the CeO2-contained samples. or reduced oxides) [13, 14]. Therefore, the coverage of
The oxidation of carbon deposition on the reduced Fe2O3/ reduced iron species by carbon deposition should result in
Al2O3 sample is very slow at the first 12 min and produces low carbon oxidation rate at the early stage of oxidation
very limited CO. Thereafter, the reaction rate increases process. The carbon conversion is strongly enhanced when
sharply and significant amount of CO is detected. CO2 the active centers become more exposed due to the removal
gradually becomes the main product in the end of the of the surface carbon. For the CeO2-contained samples,
reaction, and the whole reaction lasted more than 25 min. there should be abundant exposed reduced cerium species
By contrast, the removal of carbon over the Fe2O3/ which is also active for carbon oxidation [14]. This can be
Ce0.7Zr0.3O2 and the Ce0.7Zr0.3O2 samples is very fast used to explain the relative oxidation rate of carbon on the
(which was finished in 10 min) and generates significant CeO2-contained samples.
quantities of CO. For the Fe2O3/CeO2 sample, the forma- Figure 6 shows the TEM images of the CeO2–Fe2O3 and
tion rate of CO is also very faster than that toward the Fe2O3/Ce0.7Zr0.3O2 after catalyzing methane decomposi-
Fe2O3/Al2O3 sample, but it is slower than that toward the tion. It is clear that part of the CeO2–Fe2O3 particles (dark
two Ce0.7Zr0.3O2-contained samples. This is related to the parts in Fig. 6a, b) is surrounded by the carbon layer
contact states between carbon deposition and catalyst par- (bright parts in Fig. 6c, d). On the other hand, it is a loose
ticles, which will be discussed in the next text. As dis- contact between the carbon deposition (bright parts in
cussed above, since the reduced iron species are the active Fig. 6c, d) and the reduced Fe2O3/Ce0.7Zr0.3O2 particles
sites for methane decomposition, carbon deposition is more (dark parts in Fig. 6a, b). This indicates that the presence of

Fig. 6 TEM images of CeO2–Fe2O3 a, b and Fe2O3/Ce0.7Zr0.3O2 c, d after methane decomposition

Rare Met. (2014) 33(2):230–238 123

236 X.-L. Sang et al.

the Ce0.7Zr0.3O2 solid solution may induce the growth 3.4 Effect of Zr contents
direction of the carbon filament, making the catalyst par-
ticles not to be surrounded by the carbon filament. In this The above investigations suggest that the Ce–Zr–O solid
case, there should be more exposed active centers (reduced solution plays a very important role in both methane oxi-
cerium and iron sites) on the reduced Fe2O3/Ce0.7Zr0.3O2 dation and carbon selective oxidation. The effect of Zr
sample for catalyzing the selective oxidation of carbon to contents on the reactivity of the Fe2O3/Ce1-xZrxO2
CO, giving rise to higher oxidation rate of carbon over this (x = 0.1, 0.2, 0.3, and 0.4) samples was also investigated.
sample, as shown in Fig. 5. Figure 7 shows the CO and CO2 concentration during the
It is generally accepted that the oxidation of carbon in isothermal reaction between methane and Fe2O3/Ce1-x
oxygen atmosphere to CO2 or CO depends on the oxygen ZrxO2 samples at 700 °C.
partial pressure, and the CO2/CO mol ratio increases It is clear from Fig. 7 that the reactivity of the Fe2O3/
linearly with the oxygen partial pressure. However, our Ce1-xZrxO2 samples for methane oxidation is significantly
previous study showed that the carbon could be selective affected by the Zr content. For the Fe2O3/Ce0.9Zr0.1O2
oxidized to CO under high oxygen partial pressure in the sample, both the CO and CO2 concentration are very low,
presence of reduced cerium oxides, because the cerium indicating poor reactivity for methane conversion. With the
oxides could be selective oxidized carbon deposition to Zr content increasing, the formation of the CO2 and CO
CO via the solid–solid reaction [13, 14]. In the present (especially for the CO2) is strongly enhanced, which sug-
work, the average selectivity of CO in the oxidation gests higher methane conversion. This suggests that the
products for the Ce0.7Zr0.3O2 sample is as high as relative high Zr content in the Fe2O3/Ce1-xZrxO2 system is
95.8 %, which is much higher than that toward the beneficial to the methane oxidation. However, it is also
Fe2O3/Al2O3 sample (69.7 %) although the amount of noted that the selectivity of CO in the outlet gas decreases
carbon deposition over the Ce0.7Zr0.3O2 sample is much when the Zr content increases to 40 % (i.e., Fe2O3/
lower (14.2 vs. 42.3 g, smaller amount of carbon means Ce0.6Zr0.4O2) due to the high concentration of the CO2.
higher oxygen partial pressure under the same oxidation Among the four samples, the Fe2O3/Ce0.7Zr0.3O2 shows the
condition). This indicates that the presence of the Ce–Zr– best performance (both high methane conversion and CO
O solid solution can strongly improve the selective oxi-
dation of carbon to CO by O2. As such, the Fe2O3/
Ce0.7Zr0.3O2 sample shows very high CO selectivity
during the carbon oxidation.
It should be noted that the oxidation process contains
eliminating carbon deposition and recruiting the lattice
oxygen of the reduced oxygen carriers (e.g., cerium sub-
oxides and/or reduced iron species) with oxygen. It was
reported that cerium suboxides can be easily re-oxidized to
restore their oxygen deficiency in oxidation atmosphere
[33–35], and the adsorption of the gaseous oxidant on the
reduced metallic sites is generally much faster than on the
carbon [28]. It is proposed that, for the oxidation of the
carbon on the catalysts to take place, O2 is first adsorbed on
the reduced sites (e.g., Ce3? or iron particles) and convert
to active oxygen species for carbon selective oxidation [13,
14]. As discussed above, the lower CO selectivity in the
products of the carbon oxidation process for the Fe2O3/
Al2O3 sample than the CeO2-containing samples indicates
that the reduced cerium species are more active than the
reduced iron species for catalyzing carbon selective oxi-
dation to CO. The formation of the Ce0.7Zr0.3O2 solid
solution could improve the reduction degree of the cerium
oxides, which would create abundant exposed active sites
(e.g., Ce3?) on the reduced Fe2O3/Ce0.7Zr0.3O2 sample.
This is the reason why the Fe2O3/Ce0.7Zr0.3O2 sample owns
a high catalytic activity for the selective oxidation of car- Fig. 7 Isothermal reaction between methane and Fe2O3/Ce1-xZrxO2
bon to CO. (x = 0.1, 0.2, 0.3, and 0.4) samples at 700 °C

123 Rare Met. (2014) 33(2):230–238

Selective oxidation of methane and carbon deposition over Fe2O3/Ce1-xZrxO2 oxides 237

selectivity) for the selective oxidation of methane to This indicates that the Zr content in the Fe2O3/Ce1-xZrxO2
syngas. has no obvious effect on their catalytic performance for
As discussed above, for the reactions between methane carbon oxidation. The earlier discussions suggest that the
and Fe2O3/Ce1-xZrxO2 to take place, the free iron species concentration of the reduced cerium sites is very important
play a role in methane activation and the Ce1-xZrxO2 solid for the carbon oxidation. The O2 is first adsorbed on the
solution provides the active lattice oxygen for the oxidation reduced cerium sites (e.g., Ce3?) and converted to active
of the activated methane to CO and H2. Since the increase oxygen species for carbon selective oxidation. The more
of the Zr content may improve the oxygen mobility of the addition of Zr4? may improve the reduction degree of the
Ce–Zr–O solid solution by forming more oxygen vacancies cerium oxides in the mixed oxides, but it also reduces the
[17], the Fe2O3/Ce1-xZrxO2 with relatively higher Zr content of CeO2. As a result, the reduction treatment by
contents show higher activity for methane oxidation. On methane may create similar concentration of the reduced
the other hand, the formation of oxygen vacancies can also cerium sites over the different Fe2O3/Ce1-xZrxO2 samples,
result in abundant surface adsorbed oxygen on the mate- which leads to the similar catalytic activity for the oxida-
rials which is very active for the complete oxidation of tion of carbon deposition to CO.
methane. As such, the CO2 concentration is much higher
for the sample with a higher Zr content, which results in a
decline of the CO selectivity with the Zr content 4 Conclusion
increasing.
The oxidation of carbon deposition on the reduced Comparative studies were performed on the reactivity of
Fe2O3/Ce1-xZrxO2 was also investigated, as shown in Fe2O3/Al2O3, Fe2O3/CeO2, Ce0.7Zr0.3O2, and Fe2O3/Ce1-x
Fig. 8. All the experiment condition remains consistent ZrxO2 (x = 0.1–0.4) oxides for methane oxidation by gas–
with that performed in Fig. 5. It can be seen that all the solid reaction and their catalytic performance for the selective
samples show similar trends toward the CO and CO2 oxidation of carbon deposition to CO. The results show that
concentration in the oxidation process, and the CO selec- Fe2O3-contained samples (i.e., Fe2O3/Al2O3, Fe2O3/CeO2,
tivity of the outlet gas for each sample is higher than 96 %. and Fe2O3/Ce1-xZrxO2) present higher activity for methane
oxidation than the Ce0.7Zr0.3O2 solid solution, while the CeO2-
contained samples (i.e., Ce0.7Zr0.3O2, Fe2O3/CeO2, and Fe2O3/
Ce1-xZrxO2) reveal much higher CO selectivity than the
Fe2O3/Al2O3 sample. This indicates that the iron species may
be the active sites for methane activation during the gas–solid
reaction and the cerium oxides provide the oxygen source for
methane selective oxidation.
CeO2-contained samples show higher CO selectivity in
the oxidation processes of the carbon deposition than the
Fe2O3/Al2O3 sample, which indicates that the reduced
cerium species should be more active than the iron species
for carbon oxidation to CO. It is observed that numbers of
carbon deposition tightly surround the reduced Fe2O3/CeO2
particles after the methane decomposition, while it is a
loose contact between the formed carbon filament and the
reduced Fe2O3/Ce0.7Zr0.3O2 catalyst. This suggests that the
presence of the Ce0.7Zr0.3O2 solid solution could change
the contact mode between the carbon deposition and the
catalysts, which results in a much higher oxidation rate of
carbon deposition over the Fe2O3/Ce0.7Zr0.3O2 sample than
that over the Fe2O3/CeO2 sample. In addition, the Fe2O3/
Ce0.7Zr0.3O2 also represents much higher selectivity for the
conversion of carbon to CO than the Fe2O3/CeO2 sample.
This can be attributed to the more abundant reduced
cerium sites on this sample. The reactivity of the Fe2O3/
Ce1-xZrxO2 samples for methane oxidation can be
Fig. 8 Carbon oxidation with oxygen over Fe2O3/Ce1-xZrxO2 improved by increasing the Zr content, but it would
(x = 0.1, 0.2, 0.3, and 0.4) samples at 700 °C reduce the CO selectivity in the products. Among the four

Rare Met. (2014) 33(2):230–238 123

238 X.-L. Sang et al.

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