Applied Catalysis B: Environmental 1326 (2002) 1–12

The removal of carbon monoxide by iron oxide nanoparticles

Ping Li, Donald E. Miser, Shahryar Rabiei, Ramkuber T. Yadav,
Mohammad R. Hajaligol∗
Research Center, Philip Morris USA, Richmond, VA 23234, USA
Received 9 August 2002; received in revised form 7 November 2002

Abstract
NANOCAT® Superfine Fe2 O3 nanoparticles were evaluated both as a catalyst and as an oxidant for carbon monoxide
oxidation. It was found that the nanoparticles are much more effective as carbon monoxide catalysts than the non-nano oxide
powder. For the Fe2 O3 nanoparticles, the reaction order is first-order with respect to the partial pressure of carbon monoxide,
and zero-order with respect to the partial pressure of oxygen. The apparent activation energy was 14.5 kcal mol−1 and the
normalized reaction rate was 19 s−1 m−2 at 300 ◦ C. In the absence of oxygen, Fe2 O3 nanoparticles oxidize carbon monoxide
directly as an oxidant. The resulting reduced forms of Fe2 O3 also catalyze a disproportionation reaction for a considerable
amount of carbon monoxide. The significant amount of carbon monoxide it can remove through the catalytic oxidation,
direct oxidation, and the disproportionation reaction make it a very promising material in certain special applications, such
as removing the carbon monoxide from a burning cigarette, where the potential toxicity of other, more conventional catalysts
would be undesirable. The higher activity of Fe2 O3 nanoparticles over non-nano Fe2 O3 powders was attributed to a small
particle size (3 nm), the presence of an hydroxylated phase of iron oxide (FeOOH), as revealed by both high resolution
transmission electron microscopy (HRTEM) and a comparable study of FeOOH (goethite) powder.
© 2002 Published by Elsevier Science B.V.
Keywords: Nanoparticles; Iron oxide; Iron hydroxide; Catalysis; Carbon monoxide; Oxidation; Disproportionation reaction; Kinetics

1. Introduction particle metal oxide is NANOCAT® Superfine Fe2 O3

Transition metal oxides are less costly alternatives
to the precious metals-based catalysts for carbon
monoxide oxidation. Nanophase transition metal ox-
ides, with small particle size, high surface area, and
perhaps more importantly, more densely populated
surface coordination unsaturated sites, could poten-
tially provide significantly improved catalytic per-
formance over non-nano catalysts. One such nano-
∗ Corresponding author. Tel.: +1-804-274-2419;
fax: +1-804-274-2891.
E-mail address: mohammad.r.hajaligol@pmusa.com
(M.R. Hajaligol).
nanoparticles (referred as NANOCAT® hereafter),
manufactured by Mach I Inc., with a particle size
of only 3 nm. NANOCAT® has been studied as a
catalyst for the direct coal liquefaction (DCL) pro-
cess [1–3]. However, its catalytic activity for car-
bon monoxide oxidation has not yet been evaluated
against other forms of iron oxide catalysts, supported
or un-supported.
Amongst the readily available carbon monoxide
oxidation catalysts, iron oxide based catalysts are es-
pecially attractive candidates in certain special appli-
cations, such as the removal of carbon monoxide in a
burning cigarette, where the potential toxicity of other
catalysts is a concern. A special interest comes from

0926-3373/02/$ – see front matter © 2002 Published by Elsevier Science B.V.

PII: S 0 9 2 6 - 3 3 7 3 ( 0 2 ) 0 0 2 9 7 - 7
2 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12
the dual functions of iron oxide as a catalyst of carbon
monoxide oxidation in the presence of oxygen, and,
in absence of oxygen, as a direct carbon monoxide
oxidant by losing the lattice oxygen. Furthermore, the
resulting reduced forms of iron oxide could catalyze
the disproportionation reaction of carbon monoxide,
with the less harmful carbon and carbon dioxide as
products.
In this work, NANOCAT® was characterized both
as a catalyst and as an oxidant of carbon monoxide
oxidation. In the catalytic oxidation, the reaction or-
ders and the activation energy were measured by flow
tube methods. The results demonstrate NANOCAT®
is a considerably superior catalyst than the other forms
of iron oxide catalysts in terms of activation temper-
ature and conversion efficiency. In direct oxidation,
the stoichiometry of the reaction and the contribution
of the disproportionation reaction to the total carbon
monoxide removal were analyzed. The structures of
NANOCAT® and its reduced forms after the direct ox-
idation were investigated by the HRTEM. The chemi-
cal and structural attributes that make NANOCAT® a
more active CO catalyst than other forms of iron oxide
are also discussed.
2. Experimental
Experiments were carried out by using a quartz flow
tube reactor (length 50 cm, i.d. 0.9 cm). A schematic
diagram is shown in Fig. 1. A piece of quartz wool
dusted with known amount of NANOCAT® was
placed in the middle of the flow tube, sandwiched by
the other two clean pieces of quartz wool. The quartz
Fig. 1. Schematics of the flow tube reactor setup.
flow tube was then placed inside a Thermcraft furnace
controlled by a temperature programmer. The sam-
ple temperature was monitored by an Omega K-type
thermocouple inserted into the dusted quartz wool.
Another thermocouple was placed in the middle of
the furnace, outside the flow tube, to monitor and
record the furnace temperature. The temperature data
were recorded by a Labview-based program. Since
the catalytic oxidation of CO is very exothermic, the
catalyst’s temperature could be significantly higher
than the heating furnace’s temperature, depending on
CO concentration and the flow rate. In this paper,
the catalyst’s temperatures are used in all plots and
kinetic calculations.
The inlet gases were controlled by a Hastings digi-
tal flow meter. The gases were mixed before entering
the flow tube. The effluent gas was analyzed either by
an NLT2000 multi-gas analyzer (non-disperse near in-
frared detector for carbon monoxide and carbon diox-
ide, paramagnetic detector for oxygen), or a Balzer
Thermal Star quadrupole mass spectrometer through
a sampling capillary. When the mass spectrometer
was used as the monitor, a 15% contribution from
the fragmentation of carbon dioxide (m/e = 44) to
carbon monoxide (m/e = 28) had been accounted for.
The NANOCAT® was purchased from Mach I Inc.
(King of Prussia, PA). The average particle size is
3 nm, according to the manufacturer. The sample was
used without further treatment. The FeOOH (goethite)
was purchased from Aldrich, the average particle size
after dry grinding was 4.5 ␮m. The ␣-Fe2 O3 was also
from Aldrich with an average particle size of 5 ␮m.
It was used without further treatment. The carbon
monoxide (4%), and oxygen (21%) gases, all balanced
 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12
with Helium, and mixtures of 3.44% carbon monoxide
with 20.6% oxygen, also balanced with helium, were
purchased from BOC Gases with certified analysis.
For HRTEM, the sample was lightly crushed and
suspended in methanol. The resulting suspension was
applied to lacey carbon grids and allowed to evaporate.
The sample was examined with a Philips-FEI Tech-
nai field emission transmission electron microscope
operating at a 200 kV accelerating potential. Images
were recorded digitally with a Gatan slow scan camera
(GIF). EDS spectra were collected with a thin window
EDAX spectrometer.
3. Results and discussion
3.1. Structure of NANOCAT®
NANOCAT® is a brown colored, free flowing pow-
der with a bulk density of only 0.05 g cm−3 . Powder
X-ray diffraction patterns of NANOCAT® revealed
only broad, indistinct reflections, suggesting that the
material was either amorphous or of a particle size
too small for this method to resolve. HRTEM, on the
other hand, is capable of resolving atomic lattices
regardless of particle size, and was employed here
to image the lattices directly. The HRTEM analyses
indicated that NANOCAT® consisted of at least two
separate phases of different grain sizes. One pop-
ulation of grains, constituting the majority of the
particles, possessed diameters of 3–5 nm. The other
size fraction consisted of particles that were much
larger with diameters of up to 24 nm. Both can be
seen in Fig. 2. The high-resolution lattice images of
the larger-grained population showed them to be well
crystalline with the structure of maghemite (g-Fe2 O3 ).
The HRTEM image of smaller particles suggested a
mix of glassy (amorphous) structure and crystalline
particles. These crystalline phases were possibly the
trivalent iron phases FeOOH and/or Fe(OH)3 . The
hydrous components of NANOCAT® could con-
tribute to its higher catalytic activity than the other
commercially available Fe2 O3 .
3.2. NANOCAT® as a carbon monoxide catalyst
The effectiveness of NANOCAT® over the non-
nano Fe2 O3 powder as a catalyst for carbon monoxide
oxidation is obvious, as shown in Fig. 3. An amount of
3
Fig. 2. HTEM image of the NANOCAT® Fe2 O3 nanoparticle
showing both crystalline and amorphous domains.
50 mg of the NANOCAT® can catalyze oxidation of
almost 100% of the carbon monoxide to carbon diox-
ide at 350 ◦ C in an inlet gas mixture of 3.44% carbon
monoxide and 20.6% oxygen at 1000 ml min−1 . Under
identical conditions, the same amount of the ␣-Fe2 O3
powder with a particle size of 5 ␮m, can only catalyze
oxidation of less than 5% of the carbon monoxide to
carbon dioxide. In addition to that, the initial light
off temperature for NANOCAT® is more than 100 ◦ C
lower than that of ␣-Fe2 O3 powder. Because the bulk
density of NANOCAT® is much smaller than that of
␣-Fe2 O3 , both NANOCAT® and ␣-Fe2 O3 powders
were dusted onto the quartz wool so that the volumes
of the catalysts in the flow tube were the same, and
thereby fixing residence times to be the same as well.
To test the thermal stability of NANOCAT® , a second
and a third run was performed after the reactor was
completely cooled down to ambient temperature. The
data is shown in Fig. 3. In the second run, the whole
conversion curve shifted upward to a higher temper-
ature region by about 50 ◦ C. The upward shifting of
the conversion curve continues in the third run, but to
a much lesser degree. Despite the upward shifting, the
performance of the NANOCAT® in the second and the
third run are still much better than the performance of
␣-Fe2 O3 . The carbon monoxide conversion rates are
4 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12

Fig. 3. Comparison of the carbon monoxide conversion efficiencies between NANOCAT® and ␣-Fe2 O3 powder. Flow rate: 1000 ml min−1 ;
CO: 3.44 vol.%; O2 : 20.6 vol.%; balanced with helium. Heating rate: 12 ◦ C min−1 ; mass of catalyst: 50 mg.

still higher than 90% in the second and the third run.
The upward shifting of the conversion curve is related
to the decomposition of the FeOOH component in the
NANOCAT® . More detailed discussion in this aspect
will be presented in a later section.
To further test the thermal stability of the
NANOCAT® , another run was performed by increas-
ing and then holding the catalyst’s temperature at
340 ◦ C with the same gas inlet as in Fig. 3. The car-
bon monoxide conversion was stable at above 90%
for more than four hours. The furnace’s temperature
was 230 ◦ C during the run.
3.2.1. Reaction order of carbon monoxide and oxygen
The reaction order of carbon monoxide was mea-
sured isothermally at 244 ◦ C. At this temperature, the
carbon monoxide to carbon dioxide conversion rate
is about 50%. With a total flow rate of 400 ml min−1 ,
the inlet oxygen was kept constant at 11% while
the inlet carbon monoxide concentration was varied
from 0.5 to 2.1%. The corresponding carbon diox-
ide concentration in the outlet was recorded and the
data are shown in Fig. 4. The linear relationship be-
tween the effluent carbon dioxide concentration and
the inlet carbon monoxide concentration indicated
that the catalytic oxidation of carbon monoxide on
NANOCAT® is first-order with respect to carbon
monoxide.
The reaction order of oxygen was measured in a
similar fashion and also shown in Fig. 4. Care was
taken to make sure that oxygen concentration was not
lower than 0.5 of the carbon monoxide inlet concen-
tration, based on the stoichiometry of the reaction.
The purpose was to prevent any direct oxidation of
carbon monoxide by NANOCAT® because of insuffi-
cient oxygen. The temperature was fixed at 244 ◦ C but
the total flow rate was increased to 1000 ml min−1 in
order to maintain the carbon monoxide conversion at
about 50%. The increase of the oxygen concentration
had very little effect on the carbon dioxide production
in the effluent gas. Therefore, it can be concluded that
the reaction order of oxygen is approximately zero.
Walker et al. [4] also observed first-order reaction for
the overall catalytic carbon monoxide reaction on 100
mesh Fe2 O3 /TiO2 .
3.2.2. Apparent activation energy and
pre-exponential factor of catalytic reaction
Since the reaction is first-order for carbon monoxide
and zero-order for oxygen, the overall reaction is a
first-order reaction. In the plug-flow tubular reactor,
the reaction rate constant, k (s−1 ), can be expressed
 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12 5

Fig. 4. Measurement of the reaction order for carbon monoxide and oxygen. For reaction order of carbon monoxide (open circle). Flow rate:
400 ml min−1 ; CO: 0.5–2.1 vol.%; O2 : 11 vol.%; balanced with helium. Temperature: 244 ◦ C; mass of NANOCAT® : 50 mg. For reaction
order of oxygen (solid circle). Flow rate: 400 ml min−1 ; CO: 0.79 vol.%; O2 : 0.4–1.6 vol.%; balanced with helium. Temperature: 244 ◦ C;
mass of NANOCAT® : 50 mg.

as [5] pre-exponential factor A can be calculated from the in-

u  C  tercept, as the example shown in Fig. 5. The measured
0
k= ln (1) values of A and Ea are tabulated in Table 1, along with
V C
values reported in the literature. The average Ea value
where u is the flow rate in ml s−1 , V the total volume of 14.5 kcal mol−1 is larger than the typical activa-
of the catalyst in cm3 , C0 the volume percentage of tion energy of the supported precious metal catalysts
carbon monoxide in the gas inlet, and C is the volume (<10 kcal mol−1 ). However, it is smaller than those of
percentage of carbon monoxide in the gas outlet. non-nano Fe2 O3 powder (≈20 kcal mol−1 ). With the
According to the Arrhenius equation: measured Ea and A, the reaction constant k can be cal-
culated according to Eq. (2), as 19 s−1 m−2 at 300 ◦ C.
k = A e−(Ea /RT) (2) NANOCAT® is more active than other supported
where A is the pre-exponential factor in s−1 , Ea the iron oxide catalysts in two ways. First, the onset
apparent activation energy in kJ mol−1 , R the gas con- temperature is at least 100 ◦ C lower (150 ◦ C versus
stant, and T is the absolute temperature in Kelvin. 250 ◦ C). Secondly, the CO conversion efficiency is
Combining the Eqs. (1) and (2), we get higher. For example, 50 mg of NANOCAT® can con-
  vert all of the CO gas (3.44% CO in 1000 ml min−1
V Ea flow) to CO2 at 350 ◦ C. At the same temperature,
ln[−ln(1 − x)] = ln A + ln − (3)
u RT 1000 mg of Fe2 O3 /TiO2 can only convert about ten
where x is the carbon monoxide to carbon dioxide percent of the CO (2.7% CO at 1000 ml min−1 flow)
conversion rate: to CO2 .
The fact that the small mass of NANOCAT® can
C0 − C
x= (4) provide high carbon monoxide conversion efficiency
C0 can probably be attributed, at least partially, to its
By plotting ln[−ln(1 − x)] versus 1/T, the apparent ac- small particle size of 3 nm and high surface area of
tivation energy Ea can be read from the slope and the 250 m2 g−1 . However, the high surface area alone
6 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12

Fig. 5. Measurement of the apparent activation energy Ea and the pre-exponential factor A. Flow rate: 300 ml min−1 ; CO: 1.1 vol.%; O2 :
14 vol.%; balanced with helium. Heating rate: 12 ◦ C min−1 ; mass of NANOCAT® : 50 mg.

cannot explained why, for the first run, the onset tem-
perature of the NANOCAT® is at least 100 ◦ C lower
than the onset temperatures of iron oxide powder, sup-
ported or unsupported. The lower onset temperature is
also reflected in the lower activation energy. The shift-
ing of the conversion curve to the higher temperature
in the second run, as shown in Fig. 3, indicates that
FeOOH component present in NANOCAT® could
be the active component responsible for the lower
onset temperature. FeOOH loses water to form Fe2 O3

Table 1
Summary of the activation energies and pre-exponential factors
Flow rate (ml min−1 ) Carbon monoxide (%) Oxygen (%) A0 (s−1 ) Ea (kcal mol−1 )

1a 300 1.32 1.34 9.0 × 107 14.9

2a 900 1.32 1.34 12.3 × 107 14.7
3a 1000 3.43 20.6 3.8 × 107 13.5
4a 500 3.43 20.6 5.5 × 107 14.3
5a 250 3.42 20.6 9.2 × 107 15.3
Average 8.0 × 107 14.5
Reference
Gas phaseb 39.6
2% Au/TiO2 c 7.6
2.2% Pd/Al2 O3 d 9.6
Fe2 O3 e 26.4
Fe2 O3 /TiO2 e 19.4
Fe2 O3 /Al2 O3 e 20.0
a This work.
b From [6].
c From [7].
d From [8].
e From [4].
 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12
Fig. 6. Direct oxidation of carbon monoxide by NANOCAT® (solid line), FeOOH (broken line), and ␣-Fe2 O3 (dashed line). Flow rate:
200 ml min−1 ; CO: 4 vol.% (vol.); balanced with helium. Heating rate: 6 ◦ C min−1 ; NANOCAT® : 50 mg; FeOOH: 100 mg; ␣-Fe2 O3 : 100 mg.
during the first run. It is no longer available for the
second run hence the shifting of the conversion curves.
Generally, the catalytic oxidation of carbon monoxide
by metal oxides can be broken down into two steps:
MO + CO = M + CO2
M + 21 O2 = MO
where M is the metal.
The first step of the catalytic reaction is for MO
to lose one oxygen atom to carbon monoxide to form
carbon dioxide. The tendency of MO to lose one oxy-
gen atom to carbon monoxide should be an impor-
tant factor in determining how good a catalyst MO
is. The MO reaction with carbon monoxide in the ab-
sence of oxygen can be checked experimentally. Fig. 6
shows the temperature scans of the Eq. (5) reaction
for NANOCAT® , ␣-Fe2 O3 , and a pure FeOOH pow-
der from Aldrich, which has a particle size of 4.5 ␮m
after dry grinding. In Fig. 8, carbon dioxide produc-
tion is used as the indicator of the reaction progress.
It can be seen that despite the vastly different particle
sizes (3 nm versus 4.5 ␮m) the traces of NANOCAT®
and FeOOH are remarkably similar and the onset tem-
peratures are very close. On the other hand, the onset
temperature for ␣-Fe2 O3 is significantly higher and
the general curve shape is quite different as well. The
7
onset temperatures for NANOCAT® and ␣-Fe2 O3 al-
most mimic those in Fig. 3. The reason that FeOOH
is easier than ␣-Fe2 O3 to lose oxygen is probably be-
cause FeOOH has a slightly longer Fe-O bondlength
and thus a slightly weaker Fe–O bond. The Fe–O
(5)
bondlength in FeOOH is 2.103 Å [9]. In ␣-Fe2 O3 , it
(6) is 2.08 Å [10]. Therefore, it is reasonable to conclude
that the FeOOH component present in NANOCAT®
provides the catalytic activity at low temperatures and
the small particle size provides the high conversion
efficiency.
3.3. NANOCAT® as direct carbon
monoxide oxidant
In the absence of oxygen, Fe2 O3 can also behave as
a reagent to oxidize carbon monoxide to carbon diox-
ide with sequential reduction of the Fe2 O3 to produce
reduced phases such as Fe3 O4 , FeO and Fe [11]. This
property is important in certain potential applications,
such as a burning cigarette, where the amount of oxy-
gen present is insufficient to oxidize all the carbon
monoxide present. In such instances, the Fe2 O3 can be
used as a catalyst first, then used again as an oxidant,
and then destroyed. In this way, a maximum amount
of carbon monoxide can be converted to carbon
8 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12

dioxide with only a minimal amount of Fe2 O3 added The net equation is
to the system.
Fe2 O3 + 3CO = 2Fe + 3CO2 (10)
The reaction of NANOCAT® with carbon monox-
ide in the absence of oxygen is quite complicated. The proportions of carbon monoxide consumed in
First, the Fe2 O3 will be reduced stepwise to Fe, as the these three steps described by Eqs. (7)–(9) are 1:2:6,
temperature increases: respectively. Also, the freshly formed Fe can catalyze
3Fe2 O3 + CO = 2Fe3 O4 + CO2 (7) the disproportionation reaction of carbon monoxide
[12–14]. The reaction produces carbon dioxide and a
2Fe3 O4 + 2CO = 6FeO + 2CO2 (8) carbon deposit:

6FeO + 6CO = 6Fe + 6CO2 (9) 2CO = C + CO2 (11)

Fig. 7. (A) Direct oxidation of carbon monoxide by NANOCAT® : the concentration of effluent carbon monoxide and carbon dioxide.
Flow rate: 200 ml min−1 ; CO: 4 vol.%; balanced with helium. Heating rate: 6 ◦ C min−1 ; mass of NANOCAT® : 59 mg. CO2 (dashed line),
CO (solid line). (B) Different plot of same data from (A) with CO consumption and CO2 production overlapped. CO2 (dashed line); CO
(solid line); CO − CO2 (broken line).
 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12
The carbon can also react with the Fe to form iron car-
bides, such as Fe3 C or Fe3 C7 , and thus deactivate the
Fe catalyst. Once the Fe is completely transformed to
iron carbide, or its surface is completely covered by
iron carbide or carbon deposit, then the disproportion-
ation reaction of carbon monoxide stops.
For the direct oxidation experiment, only 4% car-
bon monoxide balanced by helium was used in the
gas inlet. The carbon monoxide and carbon dioxide
concentrations were monitored in the effluent gas
while the temperature was increased linearly from
ambient to 800 ◦ C at the rate of 12 ◦ C min−1 . The
production of carbon dioxide and the depletion of car-
bon monoxide were almost mirror images, as shown
in Fig. 7(A). However, a more careful comparison in
Fig. 7(B) shows that the depletion of carbon monoxide
and the production of carbon dioxide are not exactly
overlapped. There is more carbon monoxide depleted
than carbon dioxide produced. The difference be-
tween the carbon monoxide depletion and the carbon
dioxide production, as indicated by the dashed line in
Fig. 7(B), starts to appear at 300 ◦ C and extends all
the way to 800 ◦ C. All of the carbon monoxide reac-
tions with different forms of iron oxide, as illustrated
by Eqs. (7)–(9), would produce the same amount of
carbon dioxide as the amount of carbon monoxide
Fig. 8. Oxidation of the reaction residues Fe, carbon deposits and carbide to Fe2 O3 and carbon dioxide. Flow rate: 180 ml min−1 ; O2 :
5 vol.%; balanced with helium. Heating rate: 6 ◦ C min−1 ; CO2 production (dashed line); O2 consumption (solid line); O2 − CO2 (broken
line).
9
consumed. However, for the disproportionation re-
action of carbon monoxide catalyzed by the reduced
forms of iron oxide as illustrated in Eq. (11), the
carbon monoxide consumed would be more than the
carbon dioxide produced, and there should be carbon
deposited on the surface.
To confirm the existence of the carbon deposit, the
reactor was first cooled down from 800 ◦ C to room
temperature under the inert atmosphere of helium gas.
Then the inlet gas was switched to 5% oxygen in he-
lium and the reactor temperature was again linearly
ramped up to 800 ◦ C. The net loss of oxygen, the
production of the carbon dioxide, and their differ-
ence are shown in Fig. 8. The corresponding reactions
are
C + O2 = CO2 (12)
4Fe + 3O2 = 2Fe2 O3 (13)
and/or
4Fe3 C + 13O2 = 6Fe2 O3 + 4CO2 (14)
The production of carbon dioxide confirms the exis-
tence of the carbon in the sample. The difference be-
tween the net loss of oxygen and the production of
carbon dioxide is the oxygen used to oxidize the Fe
10 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12

Fig. 9. HRTEM of Fe2 O3 nanoparticle heated to 800 ◦ C in the presence of 4% carbon monoxide showing graphite surrounding iron carbide.

Table 2
The stoichiometry of the carbon monoxide + Fe2 O3 reaction (unit: mmol)
Species Measured Theoretical Description
Carbon monoxide + Fe2 O3 reaction
Iron oxide 0.344 59.0 mg of NANOCAT® with 7 wt.% of water, as
measured by TG
Carbon monoxidetotal 2.075 Total carbon monoxide consumption
Carbon dioxidetotal 1.551 Total carbon dioxide production
C = COtotal − carbon dioxidetotal 0.524 Total carbon in the residue
Carbon dioxidedisprop. = C 0.524 Carbon dioxide produced from the disproportional reaction
according to Eq. (9)
Carbon dioxideFe2 O3 = carbon dioxidetotal − 1.027 1.032 Carbon dioxide produced according to Eqs. (5)–(7)
carbon dioxidedisprop.
Oxygen + Fe, C reaction
Oxygentotal 1.060 Total oxygen consumption in the oxidation reaction
Carbon dioxide 0.564 Carbon dioxide production from the oxidation of
carbon deposit
C = carbon dioxide 0.564 Total carbon content in the residues
OxygenFe2 O3 = oxygentotal − C 0.496 0.516 The oxygen used to oxidize Fe to Fe2 O3
 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12
back to Fe2 O3 . This was also supported by the color
change of the sample from black to bright red.
As a further check, a sample heated to 800 ◦ C in the
presence of carbon monoxide and He was quenched
and examined with high-resolution TEM with energy
dispersive spectroscopy. Essentially, two phases were
observed, an iron-rich phase and carbon. These phases
are shown in Fig. 9. The iron-rich phase formed a nu-
cleus for the precipitation of the carbon. The lattice
fringes of the carbon have a 3.4 Å spacing, verifying
that the carbon is graphite. The iron-rich core produced
EDS spectra indicating only the presence of iron and
carbon. The lattice fringes in Fig. 9 could be indexed
as the metastable iron carbide Fe7 C3 with Pnma sym-
metry. Lattices of other crystals match Fe3 C. A hard
mass was found on the bottom of the reactor tube. Ex-
amination of this material in the TEM indicated that
it consisted of a mixture of iron carbide, graphite, and
essentially pure iron.
The carbon monoxide disproportionation reaction is
also effective in carbon monoxide removal. A detailed
stoichiometric account of the reduction and oxidation
reactions is given in Table 2. In the CO + Fe2 O3 reac-
tion, the difference between the total carbon monoxide
consumption (COtotal ) and the total carbon dioxide
production (carbon dioxidetotal ) of 0.524 mmol can
be attributed to the formation of the carbon deposits
Fig. 10. Direct oxidation of carbon monoxide by NANOCAT® : the stepwise reduction of Fe2 O3 (see text for explanation).
11
and iron carbides according to Eq. (11). This is in
reasonable agreement with the 0.564 mmol deter-
mined by the oxidation of the reaction residue. The
carbon dioxide produced from the reduction of Fe2 O3
(carbon dioxideFe2 O3 ), is the difference between the
carbon dioxidetotal and the carbon dioxide produced
from the carbon monoxide disproportionation reaction
(carbon dioxidedisprop. ). The 1.027 mmol of carbon
dioxideFe2 O3 agrees very well with the 1.032 mmol
calculated from the initial amount of Fe2 O3 , accord-
ing to Eq. (10). In the O2 + (Fe, Fe3 C, and C) oxida-
tion reactions, the oxygen spent on the oxidation of
the Fe species to Fe2 O3 also agrees very well with the
oxygen needed as calculated from the Eqs. (12)–(14).
It is interesting to observe the extent to which the
disproportionation reaction of carbon monoxide pro-
ceeded. The amount of total carbon monoxide con-
sumed (COtotal ) of 2.075 mmol is more than double
that of the carbon monoxide consumed (1.027 mmol)
by Eq. (10). Regarding the extra carbon monoxide
consumption, 50% became carbon deposits and car-
bides, and the other 50% became carbon dioxide.
Therefore, the contribution of the carbon monox-
ide disproportionation reaction to the total carbon
monoxide removal is significant.
The expected stepwise reduction of NANOCAT®
is illustrated in Fig. 10, which is a plot of the
12 P. Li et al. / Applied Catalysis B: Environmental 1326 (2002) 1–12
accumulated CO2 production at different temperature.
The contribution of the CO2 from the reaction (11)
has been subtracted out. According to Eqs. (7)–(9),
the ratio of carbon dioxide produced in these three
steps is 1:2:6. However, in Fig. 10, only two steps can
be observed with a ratio of approximately 1:7. Ob-
viously, reactions (8) and (9) are not well separated.
This is consistent with the observation that FeO is not
a stable species [11].
4. Conclusions
NANOCAT® was characterized both as a carbon
monoxide catalyst and as a carbon monoxide oxi-
dant. As a catalyst, the reaction order is first-order for
carbon monoxide and zero-order for oxygen. The ap-
parent activation energy is 14.5 kcal mol−1 . The small
particle size and the FeOOH component presented
in NANOCAT® contribute to its high performance
as a carbon monoxide catalyst, with a reaction rate
of 19 s−1 m−2 at 300 ◦ C. In the absence of oxygen,
the NANOCAT® is an effective carbon monoxide
oxidant, as it can directly oxidize the carbon monox-
ide to carbon dioxide. In addition, during the direct
oxidation process, the reduced form of NANOCAT®
catalyzed the disproportionation reaction of carbon
monoxide, producing carbon deposits, iron carbide,
and carbon dioxide. The disproportionation reaction
of carbon monoxide contributes significantly to the
total removal of carbon monoxide.
Acknowledgements
The authors would like to express thanks to the
management of Philip Morris, USA for their support
of the basic scientific research.
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