Studies on the decomposing carbon dioxide into carbon

with oxygen-decient magnetite

II. The effects of properties of magnetite on activity of
decomposition CO
2
and mechanism of the reaction
Chun-lei Zhang
a,b,*
, Shuang Li
b
, Li-jun Wang
b
, Tong-hao Wu
b
, Shao-yi Peng
c
a
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
P.O. Box 110, Dalian 116023, PR China
b
Department of Chemistry, Jilin University, Changchun 130023, PR China
c
Shanxi Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, PR China
Received 15 January 1999; received in revised form 21 June 1999; accepted 2 July 1999
Abstract
The properties of reduction and adsorption of magnetite were investigated using temperature programming technique and
thermogravimetrical (TG) analysis, and the properties of magnetite were correlated with the activity of decomposing CO
2
into carbon.
The smaller the particle size of magnetite, the larger the surface area; and the lower the activated temperature by H
2
reduction, and the
faster the activated speed (the speed of lost oxygen), the greater the amount of adsorption of O
2
and CO
2
, i.e., the higher the activity of
decomposing CO
2
is. There was specic rapid adsorption of CO
2
on Fe
3
O
4-
( > 0), with oxygen deciency and this adsorption
accompanied with decomposing CO
2
into carbon. Fe
3
O
4-
transfers its electron to the carbon in CO
2
; therefore, CO
2
decomposes into
carbon. Simultaneously, Fe
3
O
4-
captures the oxygen in CO
2
and converts itself into stoichiometric Fe
3
O
4
; so, Fe
3
O
4-
is deactivated. But
Fe
3
O
4-
could be regenerated by activating Fe
3
O
4
by H
2
reduction. The reaction of decomposing CO
2
into carbon with magnetite belongs to
quasi-catalytic reactions, and is equal to one-side reaction of the reversible process of the water gas shift reaction (WGS). Decomposition of
CO
2
into carbon on oxygen-decient magnetite undergoes via two steps: CO
2
CO O
2
and CO C O, the former step is the
control step of the reaction speed, and the intermediate product of CO is rapidly converted further into carbon. # 2000 Published by
Elsevier Science S.A. All rights reserved.
Keywords: Decomposition of CO
2
; Magnetite; Performance of reduction; Absorption properties; Mechanism of reaction; Quasi-catalytic reaction;
Deactivation; Activation by reduction
1. Introduction
Magnetite is not only a very good magnetic material, but
is also applied extensively in the catalytic eld. It is a
catalyst industrially applied in synthetic ammonia, FT
synthesis (i.e., the hydrogenation of CO to hydrocarbon,
which was rst studied by Fischer and Tropsch) [1,2],
dehydrogenation of ethylbenzene, oxydehydrogenation of
butene, and water gas shift reaction (WGS). Recently, it has
been found that oxygen-decient magnetite is a good mate-
rial to convert carbon dioxide into carbon [36], but it is not
clear about the mechanism of decomposing CO
2
to carbon
on magnetite, and there have not been reports on the relation
between the surface properties, reduction ability, adsorption
properties of magnetite and its activity of decomposition of
carbon dioxide. It is very important that carbon dioxide is
xed into carbon and indirectly converted to oxygen for
purifying the air of the sealed system and clearing away
carbon dioxide and supplying oxygen. It is also signicant to
nd out the mechanism of decomposing carbon dioxide over
magnetite and to control conditions of the activation of
magnetite by H
2
reduction.
The preparation of oxygen-decient magnetite and its
activity of decomposing CO
2
into C has been reported in our
previous paper [5]. In the present paper, we discussed
emphatically the properties of magnetite (surface area,
Materials Chemistry and Physics 62 (2000) 5261
*
Corresponding author. Tel.: 86-411-469-4447; fax: 86-411-
4691570
E-mail address: xucui@ms.dicp.ac.cn (C.-l. Zhang)
0254-0584/00/$ see front matter # 2000 Published by Elsevier Science S.A. All rights reserved.
PII: S0 2 5 4 - 0 5 8 4 ( 9 9 ) 0 0 1 6 8 - 6
ability of reduction and properties of thermal desorption of
adsorbed O
2
and CO
2
) and their effects on the activity of
decomposing CO
2
into C. Based on the structure of mag-
netite analysed before and after decomposition of CO
2
with
the magnetite, the mechanism of reaction was proposed.
The deactivation and regeneration of the magnetite were
investigated; moreover, it was compared to the process of
water gas shift reaction.
2. Experimental
2.1. Measurement of surface area of magnetite
The adsorption isotherm of N
2
gas of the sample was
measured by ASAP-2000 automatic physical adsorption
instrument, and the surface area was calculated by BET
method.
2.2. Measurement of reduction performance of magnetite
0.1 g of the magnetite sample, which was sieved through
the 4060 mesh, was pre-treated in N
2
at 623 K for 30 min,
and cooled to room temperature. Then, a mixture gas of H
2
/
N
2
= 1/10, at the rate of 50 ml/min was introduced. The
experimental temperature programming reduction (TPR)
was carried out at a heating rate of 10 K/min, up to
1073 K. The amount of expending H
2
was measured using
a thermal conductivity detector. The thermogravimetric
(TG) analysis used Perkin-Elemer TGA-7 thermoanalyzer.
The programming thermogravimetric analysis of H
2
reduc-
tion was carried out in hydrogen gas, with a ow velocity of
20 ml/min, from room temperature to 1073 K, with a heat-
ing rate of 20 K/min, according to the temperature program-
ming. The thermostatic thermogravimetric analysis of H
2
reduction was carried out in hydrogen gas with a ow
velocity of 20 ml/min at 573 K.
2.3. Measurement of adsorption properties of magnetite
0.5 g of the sample, which were sieved through 4060
mesh for the temperature programming desorption of
adsorbed O
2
(O
2
-TPD), was pretreated in He, with the rate
of 40 ml/min at 1073 K for l h, and oxygen was adsorbed at
room temperature, or in the process of temperature dropping
from 573 K to room temperature, and then using He,
exhausted physical adsorption of O
2
on the surface of the
sample. Thermal desorption of adsorbed oxygen was carried
out at a heating rate of 20 K/min from room temperature to
1073 K, the concentration of the desorbed gas was mon-
itored and recorded by a thermal conductivity detector. The
experimental of the TPD of adsorbed CO
2
(CO
2
-TPD) was
carried out by the same procedure as mentioned above for
O
2
-TPD.
2.4. The thermogravimetric analysis of decomposing
CO
2
with magnetite
0.1 g of the magnetite powder was reduced by H
2
at the
rate of 20 ml/min at 573 K for 100 min, and then was blown
by He for 10 min, CO
2
ow of 20 ml/min was introduced
and weight gain (TG curves) was recorded using Perkin-
Elmer TGA-7 thermal analyser. Other experimentals were
carried out by the same procedure, described in the previous
paper [5].
3. Results and discussion
3.1. Effects of the surface area of magnetite on the activity
of decomposing CO
2
Table 1 shows the BET surface area of a series of
magnetite samples and the activity of their decomposing
CO
2
. The surface area of BET increased in the order Fe
3
O
4
-
IV < Fe
3
O
4
-II < Fe
3
O
4
-III < Fe
3
O
4
-V, which correlated
inversely with the average particle size of magnetites.
The conversion of CO
2
and the amount of deposited carbon
increased with Fe
3
O
4-d
( > 0) reduced 3 h in H
2
in the order
Fe
3
O
4
-II < Fe
3
O
4
-III < Fe
3
O
4
-V < Fe
3
O
4
-IV. It is obvious
that the activity of decomposing CO
2
with Fe
3
O
4-d
related
directly to the BET surface area of magnetite, i.e., with
increasing the BET surface area, the conversion of CO
2
and
the amount of deposited carbon increased, and the partial
pressure of CO
2
and COdecreased except for Fe
3
O
4
-IV. The
BET surface area of Fe
3
O
4
-IV was the smallest among the
four samples, while Fe
3
O
4
-IVexhibited the highest activity
in decomposing CO
2
because it contained -Fe and Fe
1-X
O
(to be equal to ~ 1 of Fe
3
O
4-d
), which have very high
activity of decomposing CO
2
[7,8].
Table 1
Particle size and BET surface area of the original magnetites and activity
a
of decomposing CO
2
with magnetites samples for reduction 3 h by H
2
Samples Particle
size (nm)
BET surface
area (m
2
/g)
Conversion
of CO
2
(%)
Amount of deposited
carbon
b
(mg)
Partial pressure
of CO
2
(10
5
Pa)
Partial pressure
of CO (10
5
Pa)
Fe
3
O
4
-II 108.8 18.5 64 131.3 0.36 0.15
Fe
3
O
4
-III 28.5 25.4 70 155.3 0.30 0.12
Fe
3
O
4
-IV 135.0 1.5 100 267.8 0 0
Fe
3
O
4
-V 8.5 41.6 85 208.9 0.15 0.07
a
Time and temperature of reaction are 573 K and 180 min, respectively.
b
Deposited carbon on the 20 g of magnetite sample, Fe
3
O
4
-IV, including Fe
3
C.
C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 5261 53
3.2. The performance of reduction of magnetite and its
effects on decomposing CO
2
3.2.1. The properties of reduction of magnetite
TPR spectra of the series of magnetite samples Fe
3
O
4
-i
(i = IIV) are given in Fig. 1. The strong reduction peak of
TPR appeared at 803, 748, 733, and 693 K, respectively,
in the order of Fe
3
O
4
-II, Fe
3
O
4
-IV, Fe
3
O
4
-III and Fe
3
O
4
-V,
and the width of half-peak declined in the same order,
except that Fe
3
O
4
-II has a shoulder peak at 673 K, but their
relative area of peaks were nearly equal (1.90 0.05, see
Table 2). The initial reduction temperature declined in the
order Fe
3
O
4
-II, Fe
3
O
4
-III, Fe
3
O
4
-V, and Fe
3
O
4
-IV, and were
615, 605, 590, and 530 K, respectively. The four magnetite
samples obtained after TPR were checked by the XRD
spectra, showed that there were not only diffraction peaks
of the spinel structure of magnetite in samples, but there also
appeared stronger characteristic peaks of -Fe, and the
XRD spectra of Fe
3
O
4
-II after the shoulder peak of TPR
at 673 K has only characteristic peaks of the spinel struc-
tural compound. It indicated that the strong reduction peaks
of magnetite in the TPR spectra could be assigned to
the reduction of Fe
3
O
4
to -Fe, and the shoulder peak
of Fe
3
O
4
-II was ascribed to g-Fe
2
O
3
, reducing to Fe
3
O
4
(the reduction peak of Fe
1-X
O did not appear in Fe
3
O
4
-IV,
and was concealed in the reduction peak of Fe
3
O
4
).
Figs. 2 and 3 show the TG curves of programming reduc-
tion and thermostatic reduction of magnetites. It is evident
that the initial reduction temperature (T
i
), the nal tempera-
ture (T
f
), the relative weight loss (w/w
o
), the speed of
weight loss (v
if
) and the activation speed (O
2
) (the speed
of losing crystal oxygen is evaluated by the tangent slope of
TG curve) all declined in the order Fe
3
O
4
-II, Fe
3
O
4
-IV,
Fe
3
O
4
-III, and Fe
3
O
4
-V, and it agrees with the results of TPR.
From Tables 13, it is also seen that the parameters of
TPR (reduction temperature and width of half peak) and of
TG (activation temperature) decreases and the speed of
reductionactivation increases with declining particle size
of magnetite and increase in the surface area, except for
Fig. 1. Temperature-programmed reduction spectra of magnetite samples
of Fe
3
O
4
-i (i = IIV).
Table 2
The TPR results of magnetite samples
Sample Initial temperature
of reduction (K)
Temperature of
TPR peak (K)
Width of
half peak (K)
Relative area
of peak
Assignment
of PTR peak
Fe
3
O
4
-II 615 673 50 0.30 g-Fe
2
O
3
Fe
3
O
4
803 160 1.95 Fe
3
O
4
-Fe
Fe
3
O
4
-III 605 733 125 1.85 Fe
3
O
4
-Fe
Fe
3
O
4
-IV 530 748 210 1.85 Fe
1-X
O -Fe
Fe
3
O
4
-Fe
Fe
3
O
4
-V 590 693 110 1.90 Fe
3
O
4
-Fe
Fig. 2. The poikilothermic thermogravimetric curves of magnetite
samples of Fe
3
O
4
-i (i = IIV) under temperature-programmed reductive
conditions.
Fig. 3. The thermostatic thermogravimetric curves of magnetite samples
of Fe
3
O
4
-i (i = IIV) under reductive conditions at 573 K.
54 C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 5261
Fe
3
O
4
-IV. The difference of the reduction performance of
these magnetites was mainly due to the different particle
size and BET surface area by different preparation methods.
3.2.2. Effects of the reduction performance of magnetite on
CO
2
decomposition
As described above (Tables 13), it was known that the
activity of decomposing CO
2
(the conversion and the
amount of carbon deposited) increased in the order
Fe
3
O
4
-i (i = IIV) with the same reduction times, while
the decrease of the reductionactivation temperature (T
i
)
and the increase of the reductionactivation speed (O
2
)
of magnetites are also in the above order. Therefore, the
more easily the sample of magnetite reduces, the higher is
the CO
2
decomposing activity. This is probably due to the
larger amount of decient oxygen and the higher degree of
reduction of magnetite under the same reduction condition.
100 mg of magnetite was reduced by H
2
at the rate of
20 ml/min at 573 K for 100 min and then blown in He gas
for 10 min; nally, carbon dioxide was introduced at the rate
of 20 ml/min their TG curves are shown in Fig. 4. It can
be seen that there was a high-speed weight gain in all
samples in the initial period of CO
2
introduction. Carbon
dioxide decomposed rapidly into carbon because carbon
dioxide was adsorbed in the special sites of oxygen-decient
magnetite [6]. After the initial rapid increase, the increase in
weight gain slowed down. The total amount of weight gain
and the speed of weight gain increased in the order Fe
3
O
4
-II
<Fe
3
O
4
-III <Fe
3
O
4
-V < Fe
3
O
4
-IV. According to the above
order, the total amount of weight gain, after being passed
through CO
2
for 4 h, is 4.0, 4.4, 6.2 and 7.0%, respectively,
including the amount of oxygen gain in the crystal grating of
magnetite, the amount of carbon deposited on surface of
magnetite and a little amount of carbon in the produced
Fe
3
C (because -Fe was produced in the process of reduc-
tion). The characteristics of weight gain of Fe
3
O
4
-IVis very
different from the other three samples and is mainly due to
the presence of Fe
1-X
O and -Fe phases in sample.
3.3. The properties of adsorption of magnetite and its
effects on the activity of CO
2
decomposition
3.3.1. O
2
-TPD of magnetite samples
Fig. 5 shows the O
2
-TPD spectra of magnetite samples
(oxygen was adsorbed at roomtemperature). As can be seen,
Table 3
Results of programming TG (3031023 K) and thermostatic TG of magnetites under reduction by H
2
a
Samples Poikilothermic TG Thermostatic TG
T
i
(K) T
f
(K) w/w
0
(%) v
if
(10
3
K
1
)
O
2
(10
6
mol/min)
Fe
3
O
4
-II 648 932 28.18 0.99 2.25
Fe
3
O
4
-III 605 870 28.35 1.07 2.55
Fe
3
O
4
-IV 535 903 27.64 0.75 1.85
Fe
3
O
4
-V 598 803 27.78 1.35 3.15
a
T
i
, initial activation temperature; T
f
, end reduction temperature; w/w
0
, relative weight loss; v
if
, rate of weight loss; O
2
, activated speed.
Fig. 4. The thermostatic thermogravimetric curves of active magnetite
samples obtained by passing H
2
through the magnetite of Fe
3
O
4
-i (i = II
V) under decomposing CO
2
conditions at 573 K.
Fig. 5. TPD chromatograms of oxygen from the magnetite samples of
Fe
3
O
4
-i (i = IIV) after oxygen adsorption at room temperature.
C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 5261 55
there were two desorption peaks in all samples in the range
of 298 to 1073 K; the low-temperature desorption peaks
appeared at nearly 400 8 K and the high-temperature
desorption peak appeared above 1073 K. By comparison,
there were three desorption peaks in the TPD spectra of
adsorption oxygen on magnetites at 573 K (Fig. 6), and the
value of the peaks are 410 8 K, 737 9 K and >1073 K,
respectively. It is evident that the two oxygen desorption
peaks at about 400 and 740 K arose under very different
adsorption conditions, while the peak above 1073 K main-
tained nearly the same with different adsorption conditions.
This results indicated that these two desorption peaks, at
about 400 and 740 K, may be assigned to the desorption of
oxygen species (O
2
and O

) adsorbed by magnetite, but

the desorption peaks at above 1073 K was due to the
`desorption oxygen in crystal grating' [9,10] from Fe
3
O
4
.
From Figs. 5 and 6, it is known that the peak temperatures
of the desorption peaks at low temperature are nearly
identical for various samples, and the initial desorption
temperature was about 333 K in the O
2
-TPD spectra, but
the area of the desorption peaks is greatly different. The area
of desorption peaks at low temperature increased in the
order Fe
3
O
4
-II < Fe
3
O
4
-III <Fe
3
O
4
-V, i.e., the larger the
BET surface area is, the smaller the particle size of magne-
tite is, and the larger the amount of O
2
desorption is.
Therefore, the surface properties of magnetite (surface area
and particle size) affect only the amount of adsorption or
desorption of oxygen; they seem to not affect the innate
characteristic of adsorption or desorption of oxygen (tem-
perature of peak), i.e., the essential properties of adsorption
and desorption of oxygen on these samples do not relate to
the surface properties of the samples.
3.3.2. CO
2
-TPD of magnetite samples
Figs. 7 and 8 are the TPD spectra of room temperature
adsorption CO
2
on original magnetite and samples after
TPR. The TPD spectra of the original magnetite appeared
only one desorption peak, excepting that of Fe
3
O
4
-IV, which
showed two desorption peaks, while, after TPR, there
appeared two CO
2
desorption peaks for all the samples,
and the corresponding desorption temperature of all the
samples was nearly equal, which indicated that the essential
nature of the adsorbed CO
2
on various samples is identical.
The desorbed gas species were determined by GC. For the
original samples of Fe
3
O
4
-i (i = II, III, V), only carbon
dioxide was found. For the samples after TPR, the species of
the rst desorption peak is only CO
2
, while the second peak
was determined to be the desorption of CO. It indicated that
the low temperature desorption peaks (nearly 455 K) of
CO
2
-TPD proceeded from the desorption of molecular CO
2
,
which was adsorbed reversibly on the samples, while the
higher temperature desorption peak (nearly 610 K) could be
ascribed to the desorbed CO produced by dissociative
adsorption of CO
2
.
It also can be seen from Figs. 7 and 8, the area of the low
temperature desorption peaks (i.e., the amount of deso-
rption) of original magnetites and the samples after TPR
Fig. 6. TPD chromatograms of oxygen from the magnetite samples of
Fe
3
O
4
-i (i = IIV) after oxygen adsorption at 573 K.
Fig. 7. TPD chromatograms of CO
2
from the original magnetite samples
of Fe
3
O
4
-i (i = IIV) after CO
2
adsorption at room temperature.
Fig. 8. TPD chromatograms of CO
2
from the magnetite samples obtained
by TPR of Fe
3
O
4
-i (i = IIV) in the range of 298 to 673 K after CO
2
adsorption at room temperature.
56 C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 5261
increased in the order Fe
3
O
4
-IV, Fe
3
O
4
-II, Fe
3
O
4
-III and
Fe
3
O
4
-V. Obviously, the amount of adsorption of CO
2
at
298 K (i.e., reversible adsorption amount) increased with
the increase of the BET surface area and the decrease of
particle size of magnetites. This agrees with the result of O
2
-
TPD of magnetite. All of the original magnetites, except
Fe
3
O
4
-IV, had no desorption peaks of dissociative adsorp-
tion of CO
2
, while it appeared over all the samples after
TPR. XRD patterns indicated that there were Fe
1-X
O and
-Fe in the sample of Fe
3
O
4
-IV, and Fe
3
O
4
-i (i = IIV) after
TPR produced Fe
3
O
4-
( > 0) of oxygen-decient spinel
structure and a little amount of -Fe. Therefore, it is
conrmed that the dissociative adsorption of CO
2
is a
characteristic of Fe
3
O
4-
, Fe
1-X
O and -Fe, and CO was
produced after desorption at about 600 K because of the
dissociative adsorption of CO
2
. Although only carbon mon-
oxide in the desorption product of dissociative adsorption of
CO
2
was checked by gas chromatography, elementary
carbon was produced in the process of dissociative adsorp-
tion of CO
2
. The carbon deposited on the magnetites after
CO
2
-TPD was analysed by elemental analysis (Table 4), and
the results showed that deposited carbon was not detected on
the original magnetites of Fe
3
O
4
-i (i = I, III, V), but it was
observed on the magnetites after TPR and the original
magnetite of Fe
3
O
4
-IV. It strongly supported the point that
the dissociative absorption of CO
2
was not produced on the
original magnetite (Fe
3
O
4
, > 0) and it was mainly
produced on oxygen-decient magnetite (Fe
3
O
4-
, _ 0).
Tabata et al. [11] considered that there was special adsorp-
tion of CO
2
(rapid adsorption) on the oxygen-decient
magnetite (Fe
3
O
4-
, > 0) and the adsorption was accom-
panied by production of carbon by CO
2
decomposition.
Because the Fe
3
and Fe
2
in oxygen-decient magnetite is
not distinguished, the electrons could hop between Fe
3
and
Fe
2
in the spinel structure of magnetite, being equal to the
electrons donated by both Fe
3
and Fe
2
ions, i.e., there was
oxygen deciency in the neighbourhood of both Fe
3
and
Fe
2
, after carbon dioxide was adsorbed. The electrons of
both Fe
3
and Fe
2
on the adsorption sites donated easily to
the carbon in the carbon dioxide, so carbon dioxide was
reduced. The oxygen in carbon dioxide, in the form of O
2
,
was transferred into lattice vacancy (oxygen deciency),
and carbon dioxide was decomposed to carbon and carbon
monoxide.
3.3.3. The relation between the activity of CO
2
decomposition and the adsorption properties
of magnetite
The results of O
2
-TPD and CO
2
-TPD on magnetites
indicated that the amount of adsorption of oxygen and
the amount of reversible adsorption of CO
2
increased in
the order Fe
3
O
4
-IV < Fe
3
O
4
-II< Fe
3
O
4
-III < Fe
3
O
4
-V, but
the amount of dissociative adsorption of CO
2
increased
in the order Fe
3
O
4
-II < Fe
3
O
4
-III < Fe
3
O
4
-V < Fe
3
O
4
-IV.
From Tables 1 and 4, it is seen that the conversion of
CO
2
increased in the order Fe
3
O
4
-II < Fe
3
O
4
-III < Fe
3
O
4
-
V < Fe
3
O
4
-IV under the same reduction condition of mag-
netite. It is evident that the activity of magnetite to decom-
posing CO
2
into carbon increased with increasing the
amount of dissociative adsorption of CO
2
, the amount of
reversible adsorption of CO
2
and adsorption oxygen (except
of Fe
3
O
4
-IV), which reected the effects of the adsorption
properties of magnetite on the activity of CO
2
decomposi-
tion.
3.4. Analysis of structure of magnetites before and after
CO
2
decomposition
The Mossbauer spectra for magnetite samples of Fe
3
O
4
-II
before and after CO
2
decomposition were given in Fig. 9,
there Mossbauer parameters and chemical composition
were listed in Table 5. It is obvious that the Mossbauer
spectra of oxygen-decient magnetite of Fe
3
O
4-
( = 0.1324), reduced for 5 h at 573 K, and that of original
Fe
3
O
4
-II were very similar (Fig. 9a and b), and the internal
magnetic eld and the area of peaks were slightly varied; the
internal magnetic eld of A-site and B-site were 492.2 kOe
and 459.2 kOe and shifted to 481.2 kOe and 452.3 kOe,
respectively. The area ratio, S
B
/S
A
, of these two group peaks
converted from 1.096 to 2.460, i.e., the peak area of A-site
decreased and the peak area of B-site increased. The S
B
/
S
A
= 1.096 < 2.0 of the original Fe
3
O
4
-II indicated that
there was a considerable amount of g-Fe
2
O
3
(about
21.5% Fe) in the original Fe
3
O
4
-II, a part of Fe
3
in the
spinel structure was reduced to Fe
2
in the Fe
3
O
3.8676
and
the S
B
/S
A
was above 2.0, which is oxygen decient. After
Fe
3
O
3.8676
was reacted with CO
2
for 3 h, the Mossbauer
spectrogram of sample did not change greatly (Fig. 9c), but
its internal magnetite eld was larger than that of Fe
3
O
3.8676
and smaller than Fe
3
O
4
-II (Fe
3
O
4.1086
) and the S
B
/S
A
was
1.950 ~ 2.0. The structure and phase of Fe
3
O
4
-II, which
was determined by XRD, before and after reduction indi-
cated that they were spinel structure compound yet and
the lattice constants of the original Fe
3
O
4
-II, the reduced
Fe
3
O
4
-II and the reacted Fe
3
O
4
-II were 0.8389, 0.8410 and
0.8397 nm, respectively. It is seen that the oxygen in the
crystal grating of the original Fe
3
O
4
-II in is excess because it
contains g-Fe
2
O
3
and its lattice constant is smaller than
0.8397 nm of the stoichiometric Fe
3
O
4
[12], Fe
3
O
3.8676
obtained by reducing the original Fe
3
O
4
-II for 5 h is oxygen
Table 4
The amount of carbon deposited on magnetites after CO
2
-TPD, including
the carbon in Fe
3
C
Samples
a
Deposited
carbon (mg)
Samples
b
Deposited
carbon (mg)
Fe
3
O
4
-II 0 Fe
3
O
4
-II 0.27
Fe
3
O
4
-III 0 Fe
3
O
4
-III 0.85
Fe
3
O
4
-IV 0.65 Fe
3
O
4
-IV 1.25
Fe
3
O
4
-V 0 Fe
3
O
4
-V 0.98
a
Original magnetite.
b
After TPR in the range of 298673 K.
C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 5261 57
decient and its lattice constant is larger than the stoichio-
metric Fe
3
O
4
, the lattice constant of Fe
3
O
3.8676
decomposed
CO
2
for 3 h was nearly equal to that of Fe
3
O
4
, indicating that
Fe
3
O
4-
of oxygen-decient magnetite completely con-
verted to stoichiometric Fe
3
O
4
after decomposition of
CO
2
. After reducing Fe
3
O
4
-II for 20 h, its Mossbauer
spectrogram changed greatly (Fig. 9d), there were three
groups of six-line spectrum of magnetic splitting in the
Mossbauer spectrogram, two groups of six-line spectrumfor
internal magnetic eld of 477.8 kOe and 451.0 kOe were
very similar to the original Fe
3
O
4
-II, which is due to the A-
site and B-site of the spinel structure, Its internal magnetic
eld is lower than Fe
3
O
3.8676
after reducing for 5 h and its
chemical composition is Fe
3
O
3.8277
, and the area ratio of
these two peaks is 2.596. Another group of six lines for
332.4 kOe was same as the characteristic Mossbauer spec-
trogram of -Fe and the amount of -Fe that is also checked
by XRD is 22.8%. For the sample Fe
3
O
3.8277
, after reacting
in CO
2
for 3 h at 573 K, there appeared four groups of six-
line spectrum in the Mossbauer spectra (Fig. 9e). Except the
three groups of six-line spectrum before reaction, one six-
line spectrum for internal magnetic eld of 209.2 kOe is
assigned to Fe
3
C, which is determined by XRD [6,7]. Fe
3
C
is produced by -Fe reacting with CO
2
or the deposited
carbon. When the sample further reacted with excess CO
2
for 10 h, the characteristic peak of -Fe in the Mossbauer
spectrogram disappeared, the peaks of Fe
3
O
4
and Fe
3
C
existed and the peak area of these species slightly increased,
which indicated that -Fe completely converted to Fe
3
O
4
and Fe
3
C (Fig. 9f and Table 5).
The Mossbauer spectra and corresponding parameters
for magnetite samples of Fe
3
O
4
-IV before and after reaction
Fig. 9. Room temperature Mossbauer spectra for magnetite samples of
original Fe
3
O
4
-II (a); reduced Fe
3
O
4
-II for 5 h by H
2
(b); reaction
of sample (b) with CO
2
for 3 h (c); reduced Fe
3
O
4
-II for 20 h by H
2
(d); reaction of sample (d) with CO
2
for 3 h (e); and with excess CO
2
for 10 h (f).
Fig. 10. Room temperature Mossbauer spectra for magnetite samples
of original Fe
3
O
4
-IV (a); and after reaction of (a) with CO
2
for 3 h (b).
58 C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 5261
with CO
2
were shown in Fig. 10 and Table 5. There
were three groups of six-line spectrum of magnetic splitting
and one group of two-line spectrum in the Mossbauer
spectrogram of Fe
3
O
4
-IV. It is evident that the three groups
of six-line spectrum with 485.7, 455.5, and 332.6 kOe of
internal magnetic eld should be assigned to A-site and
B-site of Fe
3
O
4
and -Fe. According to the larger IS
(IS = 1.32 mm/s) of the two-line spectrum, it should be
ascribed to the species containing Fe
2
, and Fe
1-X
O was
observed in XRD. When the sample reacted with CO
2
for 3 h without being reduced, the two-line and six-line
spectra with internal magnetic eld 332.6 kOe of Fe
3
O
4
-
IV disappeared and one group of six-line spectrum
of 209.8 kOe appeared in the Mossbauer spectrogram. It
indicated that Fe
1-X
O and -Fe had reacted with CO
2
and
converted into Fe
3
O
4
and Fe
3
C. From Table 5, it also can be
seen that the amount of Fe
3
C, which was produced in the
reaction of Fe
3
O
4
-IV with CO
2
, was larger than the amount
of -Fe in Fe
3
O
4
-IV before reaction, it indicated that the
Fe
3
C was not produced only from the reaction between
-Fe and CO
2
. In fact, Fe
1-X
O undergoes eutectoid
decomposition in the process of the decomposing CO
2
with
Fe
3
O
4
-IV and decomposes into Fe
3
O
4
and -Fe [13].
Therefore, a part of produced Fe
3
C may have come from
Fe
1-X
O.
Above analysis indicated that no matter what, Fe
3
O
4-
( > 0) of oxygen-deciency or Fe
1-X
O or -Fe were able to
decompose CO
2
into carbon and converted itself into stoi-
chiometric Fe
3
O
4
(or Fe
3
C).
3.5. An exploration of mechanism of decomposing CO
2
into carbon
3.5.1. Mechanism of CO
2
decomposition
The structure analysis of magnetite before and after
CO
2
decomposition indicated that the spinel structure of
Fe
3
O
4-
( > 0) after CO
2
decomposition was still main-
tained, but the determination of the lattice constant and
chemical composition indicated that Fe
3
O
4-
( > 0) seized
the oxygen in the CO
2
, and converted itself into stoichio-
metric Fe
3
O
4
; simultaneously, CO
2
was decomposed into
carbon. After Fe
1-X
O and -Fe react with CO
2
, they would
be converted into Fe
3
O
4
and Fe
3
C. Fe
3
O
4-
( > 0), Fe
1-X
O
and -Fe were all able to decompose CO
2
into carbon and
O
2
in the lattice of Fe
3
O
4
, i.e., CO
2
C O
2-
; therefore,
all of them are in the active phase of CO
2
decomposition.
Fe
3
O
4
CO
2

573 K
Fe
3
O
4
C( b 0)
Fe
1X
O CO
2

573 K
Fe
3
O
4
C
Fe
1X
O
573 K
Fe
3
O
4
-Fe
-Fe CO
2

573 K
Fe
3
O
4
Fe
3
C
From the studies of CO
2
decomposition [5], it was also
discovered that decomposing of CO
2
by the above active
phases not only produced carbon, but also produced a little
amount of CO. The smaller the -value of Fe
3
O
4-
, the larger
Table 5
Chemical composition and Mossbauer parameter of magnetites before and after decomposing CO
2
Sample Phase and composition IS (mm/s) QS (mm/s) H (kOe) Fe (%) S
B
/S
A
Fe
3
O
4
-II (original) Fe
3
O
4.1086
A 0.38 0.02 492.2 47.7 1.096
B 0.74 0.05 459.2 52.3
Fe
3
O
4
-II (5 h
a
) Fe
3
O
3.8676
A 0.35 0.00 481.2 28.9 2.460
B 0.61 0.00 452.3 71.1
Fe
3
O
4
-II (5 h
a
, 3 h
b
) Fe
3
O
4
A 0.37 0.01 490.5 33.9 1.950
B 0.68 0.02 455.3 66.1
Fe
3
O
4
-II (20 h
a
) Fe
3
O
3.8277
A 0.28 0.01 477.8 21.3 2.596
B 0.59 0.00 451.0 55.9
-Fe 0.01 0.00 332.4 22.8
Fe
3
O
4
-II (20 h
a
, 3 h
b
) Fe
3
O
4
A 0.38 0.00 490.2 27.6 1.978
B 0.69 0.01 456.0 54.6
-Fe 0.02 0.01 331.5 8.5
Fe
3
C 0.29 0.04 209.2 9.3
Fe
3
O
4
-II (20 h
a
, 10 h
b
) Fe
3
O
4
A 0.39 0.02 491.3 28.9 1.983
B 0.70 0.01 455.8 57.3
Fe
3
C 0.26 0.26 208.8 13.8
Fe
3
O
4
-IV (original) Fe
3
O
4.0014
A 0.42 0.00 485.7 26.5 2.064
B 0.85 0.04 455.5 54.7
Fe
1-X
O 1.32 0.21 0.00 17.1
-Fe 0.07 0.05 332.6 1.7
Fe
3
O
4
-IV (3 h
b
) Fe
3
O
4
A 0.41 0.02 488.3 30.4 1.977
B 0.72 0.01 456.2 60.1
Fe
3
C 0.33 0.01 209.8 9.5
a
Reduction time.
b
Reaction time.
C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 5261 59
the amount of CO produced. With the -value increased at
higher reaction temperature (673 K), CO was hardly
observed. According to the above results, we supposed that
CO
2
decomposes into carbon on the oxygen-decient
Fe
3
O
4-
, perhaps via two steps, i.e., CO
2
CO O
2
and CO C O
2
(the reaction 2CO C CO
2
could
hardly occur). Since the disappearance of CO always takes
precedence over disappearance of CO
2
on Fe
3
O
4-
with
larger -value, i.e., the speed of CO conversion into carbon
is faster than the speed of CO
2
conversion, it is evident that
the step of CO
2
CO O
2
could be the control step of
the reaction speed.
3.5.2. Deactivation and regeneration of decomposing
CO
2
over magnetite
It can be seen from Table 4 that the stoichiometric or
oxygen-excess magnetite (Fe
3
O
4
, _ 0) is inactive to
CO
2
decomposition. After reacting with CO
2
, Fe
3
O
4-
( > 0) converted to stoichiometric Fe
3
O
4
and thus became
deactivated. The activity of the deactivated Fe
3
O
4
can be
recovered by H
2
reduction, i.e., the magnetite after reaction
can be regenerated by H
2
and be cyclically used; the active
site of magnetite covered by depositing carbon (about 15%)
would be reactivated. There are two methods to remove
deposited carbon: chemical method rapidly reacting with
H
2
O above 773 K, i.e., C H
2
O CO H
2
; physical
method ultrasonic oscillation and centrifugalization of
the suspended solution of magnetite with deposited carbon
and then dumped in the liquid. The above-described deac-
tivation of magnetite could be regenerated, and is called
temporary deactivation. If a part of magnetite was reduced
by H
2
into -Fe or original magnetite prepared containing
-Fe or Fe
1-X
O (such as Fe
3
O
4
-IV), Fe
3
C would be pro-
duced after reaction, and Fe
3
C cannot recover to Fe
3
O
4-
( > 0) and thus become deactivated permanently.
If the preparation conditions of the magnetite and the
activation by H
2
reduction was controlled not to produce -
Fe or Fe
1-X
O, the magnetite would not be permanently
deactivated and would be able to regenerate and recover
the reactivity of decomposing CO
2
into carbon.
3.5.3. Analysis of the process of decomposing CO
2
with magnetite
From the comprehensive results of reductionactivation
of magnetite, decomposition of CO
2
, deactivation and
regeneration of magnetite, it was seen that the total process
of magnetite decomposing CO
2
can be divided into two sub-
processes (1) and (2):
Fe
3
O
4
H
2

573 K
Fe
3
O
4
H
2
OY b 0 (1)
Fe
3
O
4
CO
2

573 K
Fe
3
O
4
C (2)
CO
2
H
2

Fe
3
O
4
Y 573 K
H
2
O C (3)
It is evident that the total process, Eq. (3), of decomposing
CO
2
into C is equal to the reaction between CO
2
and H
2
that
produced H
2
O and C on the magnetite Fe
3
O
4
catalyst, but
these two sub-processes of reductionactivation of magne-
tite, Eq. (1), and decomposition reaction of CO
2
, Eq. (2),
belong to stoichiometric reaction. Therefore, the total pro-
cess, Eq. (3), of the reaction belongs to quasi-catalytic
reaction, i.e., the process of decomposing CO
2
into C is
between stoichiometric reaction and catalytic reaction. The
subsidiary reaction is
Fe
3
O
4
CO
2

573 K
Fe
3
O
4
CO (4)
Eqs. (4) and (1) were added to get Eq. (5):
CO
2
H
2

Fe
3
O
4
Y 573 K
H
2
O CO (5)
It is seen that the subsidiary reaction in the process of
magnetite decomposing CO
2
into C equals the process of
hydrogenation of CO
2
catalysed by Fe
3
O
4
; it is the rever-
sible process of water gas shift reaction, Eq. (6), on indus-
trialisation [14]. But one subsidiary reaction of reversible
process of water gas shift reaction is to produce deposited
carbon, Eq. (3), which is our purpose.
CO H
2
O
Fe
3
O
4
Y 573 K
CO
2
H
2
(6)
It is well known that Fe
3
O
4
is a good catalyst for water
gas shift reaction and it is able to efficiently catalyse
both the positive and negative reactions. Therefore, the
reaction between CO
2
and H
2
over Fe
3
O
4
mainly produced
CO and H
2
O, Eq. (5). Though Fe
3
O
4
is also active for the
reverse process of water gas shift reaction, we have carried
out by dividing it into two steps, (1) and (2), i.e., Fe
3
O
4
reduced by H
2
prepared active Fe
3
O
4-
with oxygen-defi-
ciency and Fe
3
O
4-d
decomposed CO
2
into carbon. As
studied above, carbon dioxide was efficiently decomposed
into carbon, the efficient decomposition of CO
2
to C is due
to the result of dividing the reverse reaction of water gas
shift reaction into two steps of (1) and (2), and in the process
of the reaction, the conversion of CO
2
is able to achieve
100%, and a little amount of CO produced was further
converted into carbon. This is proved to be a efficient
process.
If the water produced from the process Fe
3
O
4
reduced by
H
2
was electrolysed to H
2
and O
2
, then after separating H
2
,
O
2
can be put into the sealed cabin of spaceships to maintain
the life systems in spaceships. The purpose of decomposing
CO
2
into C over Fe
3
O
4-
is to purify the air in the cabin of
spaceships and to clear away CO
2
. After decomposing CO
2
,
Fe
3
O
4-
could be converted into Fe
3
O
4
and deactivated. The
H
2
released by electrolysing water activated Fe
3
O
4
and
converted to Fe
3
O
4-
. Thus, this process can clear away
CO
2
and supply O
2
in the spaceship. It is evident that the
nal sources of oxygen the oxygen in CO
2
, and CO
2
itself was xed to carbon after the above-described circula-
tion.
60 C.-l. Zhang et al. / Materials Chemistry and Physics 62 (2000) 5261
4. Conclusions
1. The properties of magnetite signicantly affected the
activity of decomposing CO
2
into C. The decomposition
of CO
2
increased with increase activity of the BET sur-
face area of magnetite, decreasing the particle size and
increasing the amount of adsorption O
2
and CO
2
. The
more easily magnetite is reduced, the higher the decom-
position of CO
2
into carbon under the same reduction
conditions is; the decomposition of CO
2
increased with
decreasing reductionactivation temperature and in-
creasing the speed of activation in process of TPR.
2. There was special adsorption of CO
2
on Fe
3
O
4-
and this
adsorption accompanies the decomposing CO
2
into
carbon that belongs to dissociative adsorption of CO
2
.
But Fe
3
O
4
( _ 0) occurred only with reversible
adsorption of CO
2
and adsorption state of CO
2
is
molecular in nature.
3. Fe
3
O
4-
could transfer its electron to the carbon in CO
2
and CO
2
was reduced to elementary carbon; simulta-
neously, the oxygen-deficiency of Fe
3
O
4-
could capture
oxygen in CO
2
and convert itself to stoichiometric
Fe
3
O
4
, i.e., become deactivated, and recovers the
activity of decomposing CO
2
through its reduction of
H
2
. Fe
3
O
4-d
, Fe
1-X
O and -Fe are all able to convert
CO
2
into C, but only the structure of Fe
3
O
4-
before and
after decomposing CO
2
was retained and Fe
3
O
4-
was
regenerated, but Fe
1-X
O and -Fe, after decomposing
CO
2
would convert into Fe
3
O
4
and Fe
3
C and were
deactivated permanently.
4. The reaction of decomposing CO
2
into C with
magnetite belongs to quasi-catalytic reaction, the total
process of reduction by H
2
and decomposition of CO
2
is
one-side reaction of reverse process of water gas shift
reaction. The reaction of converting CO
2
into C with
oxygen-deficient magnetite is very important to
maintain life systems in spaceships and other sealed
systems.
Acknowledgements
Financial support from the National Natural Science
Foundation of China (NNSFC 29703002) is gratefully
acknowledged.
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