molecules

Article
The Adsorption Behaviors of CO and H2 to FeO onto CaO
Surfaces: A Density Functional Theory Study
Ziming Wang 1,2, *, Yaqiang Li 1,2 , Yaping Dou 1 , Kejiang Li 3, *, Wanhai Yu 1,2 and Pengcheng Sheng 1,2

1 Department of Automotive Engineering, Hebei Vocational University of Technology and Engineering,

Xingtai 054000, China
2 Hebei Special Vehicle Modification Technology Innovation Center, Xingtai 054000, China
3 School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing,
Beijing 100083, China
* Correspondence: wangziming@[Link] (Z.W.); likejiang@[Link] (K.L.)

Abstract: The adsorption behaviors of CO and H2 to FeO onto CaO surfaces have been studied
using the density functional theory (DFT) to determine the reactions of FeO by CO and H2 . The
adsorption mechanisms of FeO clusters on the CaO(100) and CaO(110) surfaces were calculated first.
The structure of the Ca(110) surface renders it highly chemically reactive compared with the Ca(100)
surface because of low coordination. After gas adsorption, CO bonds to the O atom of FeO, forming
CO2 compounds in both configurations through the C atom. H2 favors the O atom of FeO, forming
H2 O compounds and breaking the Fe-O bond. Comparing the adsorption behavior of two reducing
gases to FeO on the Ca surface, the reaction of the CO molecule being adsorbed to generate CO2
compounds is exothermic. The reaction of H2 molecule adsorption to generate H2 O compounds is
endothermic. This property is essential for the inertial-collision stage of the reduction. However, the
dissociation of the CO2 compound from the reaction interface will overcome a high energy barrier
and slow down the reduction. The H2 O compound dissociates from the surface more easily, which
can accelerate the reduction.

Keywords: density functional theory; adsorption; H2 and CO; FeO; CaO surface

Citation: Wang, Z.; Li, Y.; Dou, Y.; Li,

K.; Yu, W.; Sheng, P. The Adsorption
Behaviors of CO and H2 to FeO onto 1. Introduction
CaO Surfaces: A Density Functional A large amount of carbon dioxide is emitted by the carbon reduction of iron ore in
Theory Study. Molecules 2023, 28, the ironmaking process. The steel industry faces enormous environmental pressures. The
5971. [Link] dominant blast furnace ironmaking process in the steel industry relies on carbon-based
molecules28165971 fuels for energy and reducing agents, resulting in large amounts of CO2 emissions into the
Academic Editor: Nino Russo environment. A key area for scientific research is the replacement of carbon with hydrogen
in green metallurgical technology. The hydrogen-enriched reduction process can use a
Received: 5 June 2023 high percentage of hydrogen to reduce iron ore to metallic iron. The product is H2 O,
Revised: 5 August 2023
which reduces the CO2 gas generated by carbon-based reduction [1–6]. The contradiction
Accepted: 7 August 2023
between the increased requirements for iron ore quality and the deterioration of iron ore
Published: 9 August 2023
quality in the hydrogen-enriched reduction process is becoming increasingly prominent.
This is a common problem that the current ironmaking process must face. An enhanced
understanding of iron oxides in the hydrogen-based reduction process is the basis for
Copyright: © 2023 by the authors.
solving this problem.
Licensee MDPI, Basel, Switzerland. There are a wealth of studies dedicated to developing an experimental understanding
This article is an open access article of the iron oxide reduction behaviors of CO and H2 [7,8]. Bahgat et al. [9] explored the
distributed under the terms and reduction of Fe3 O4 single crystals by H2 and measured an activation energy of 99 kJ mol−1 .
conditions of the Creative Commons The reaction rate slowed down at 900 and 950 ◦ C at 83% and 89% reduction, respectively,
Attribution (CC BY) license (https:// indicating rate limitation by solid-state diffusion. Chen [10] demonstrated the isotherm
[Link]/licenses/by/ reduction of Fe2 O3 with a fluidized bed and measured the activation energy required
4.0/). for the reduction to FeO and Fe at 83.6 and 80.4 kJ mol−1 , respectively. Bondale [11]

Molecules 2023, 28, 5971. [Link] [Link]

Molecules 2023, 28, 5971 2 of 10

explored the isotherm reduction of Fe2 O3 pellets with H2 /H2 –CO mixtures. It was found
that the reduction with pure H2 was faster compared with CO and gas mixtures and
both the restrictions arising from the decrease in CO content as well as those related
to gas diffusivity were revealed. Kim et al. [12] investigated the kinetics of cylindrical
compacts of magnetite (Fe3 O4 ) with H2 and H2 –H2 O (g) mixtures. The initial reduction
rate increases with H2 partial pressure. However, as the reduction proceeds, an iron
layer is formed and the rate decreases significantly. The thermodynamic analysis of the
reduction shows that hematite (Fe2 O3 ) reduction by CO and H2 leads to microstructural
evolution [7,9]. Prior reports have indicated three steps: Fe2 O3 →Fe3 O4 →FeO→Fe. The
reduction process leads to the formation of several cracks and holes in the process of
microstructural transformation [13–15]. In addition, the control step of the generation of
iron whiskers is the reduction of FeO to Fe. Moreover, when comparing the reduction
behavior of CO and H2 gases on iron oxide, the reduction rate of H2 is higher than that of
CO. The smaller size of the hydrogen atom favors the diffusion of the reducing gas, leading
to a kinetically favorable reduction [16]. The current understanding of hydrogen-based
direct reduction is limited to the macroscopic description and rate analysis of the reduction
process. The microscopic reaction mechanism and electronic structure properties of iron
oxides still lack scientific knowledge and evaluation. The mechanism of the competitive
reduction of iron oxide by CO and H2 is not clear. Previous studies have demonstrated that
the addition of CaO can control the basicity of blast furnace slag [17]. Meanwhile, CaO
covers the surface of iron ore powder to increase the separation effect [18] and avoid the
sponge iron surface reduction generated by the iron whiskers and thus leads to the sticking
problem in the fluidized bed reduction process [19,20]. However, the conversion of the
CaO and Fe2 O3 /FeO phase to the CaO–FeO phase at their interface is confirmed using
SEM/EDS measurements. FeO is sensitive to CO and H2 ; therefore, the CaO–FeO phase
behavior and reduction is interesting. Zhao et al. [21] investigated the reduction properties
of Fe2 O3 with different CaO contents in a CO atmosphere using thermogravimetric analysis.
This study suggested that the doped Ca catalyzes the reduction of Fe2 O3 by destroying the
crystal structure and facilitating the diffusion of O2 , especially as the decomposition of the
FeO phase into Fe occurs [22]. The protective effect of CaO is reduced.
The density functional theory (DFT) has been used to explore the reduction of iron
oxides. Zhong et al. [16] investigated the adsorption behavior of CO and H2 on the surface
of FeO using DFT calculations to explore the reduction mechanism. The CO molecule
binds to the O atom of the FeO surface to generate a C–O bond to produce CO2 . When
H2 adsorbs to the surface of FeO(110), the H2 molecule dissociates, forming an O–H bond
and an Fe–H bond. For the adsorption of H2 onto the FeO(111) surface, H2 adsorbs to the
O top of the FeO(111) surface and H2 O is generated. In addition, Zhong [23] used DFT
to show that CaO and MgO surfaces promote the binding of FeO to CO. Dong et al. [24]
used thermogravimetric analysis (TGA) experiments and DFT to investigate the reduction
of iron oxide, and the results indicate that the reduction of Fe2+ to Fe is the control step.
Sun et al. [25] studied the adsorption of H2 on the Fe3 O4 surface and showed that H atoms
are more likely adsorb to the O atom on the surface of Fe3 O4 rather than to Fe atoms.
Zhong used DFT theory to investigate the promotion of CaO and MgO surfaces due to
their relatively larger binding energies for the binding of CO to FeO.
The experimental results were used to study the thermodynamics and kinetics in-
volved in the reduction of iron oxide with CO and H2 , explaining the limiting step in the
reaction. However, in practice, the competitive reduction mechanism of iron oxide by
CO and H2 is not clear. More than one single CaO surface can take part in the reduction
of iron oxide processes. An atomistic insight into reducing agents’ absorption and the
dissociation of product on the CaO surface is desirable. Here, theoretical work with the
DFT was dedicated to study the reactions of FeO by CO and H2 on CaO surfaces on the
atomic scale.
 2. Results and Discussion
2.1. Adsorptions of FeO to CaO Surfaces
Molecules 2023, 28, 5971 3 of 10
Recent studies [26,27] have shown that iron oxide can be represented by cluster
Fe2O2, Fe3O4, and Fe2O3 to study the mechanism of its reduction by CO. A single Fe–O
[Link] basicand
Results structure
Discussionof complex iron oxides. Therefore, we use the FeO cluster to illus
effect
2.1. of CaOofon
Adsorptions FeO the reduction
to CaO Surfaces of FeO by CO and H2.
The interaction
Recent studies [26,27]ofhave 2 with
COshown the
that ironCaO(100)
oxide can be surface and by
represented theclusters
CaO(110)of surf
FeO, Fe
calculatedO ,
2 2 by Fe O , and
3 placing
4 Fe
theO to study the mechanism of its reduction by CO.
2 3FeO cluster onto three adsorption sites: O top, Ca top, holl A single
Fe–O bond is the basic structure of complex iron oxides. Therefore, we use the FeO cluster
bridge. The all-adsorption configurations were also tested. Considering the FeO clus
to illustrate the effect of CaO on the reduction of FeO by CO and H2 .
the CaO surface structure,
The interaction of CO2 with thetheFe atom
CaO(100)prefers to approach
surface the O top
and the CaO(110) site on
surface wasthe CaO
calculated by placing the FeO cluster onto three adsorption sites: O top, Ca top, hollow, andfor the C
while the O atom of FeO is the most energetically favorable binding partner
bridge. The all-adsorption
The optimized geometry configurations were also tested.
of FeO adsorption onto theConsidering
CaO surface the FeO is clusters
shown in Fig
and the CaO surface structure, the Fe atom prefers to approach
the interface, the bond distances of Fe–O and O–Ca are 2.30 Å and 1.90 Å, the O top site on the CaOrespectiv
surface, while the O atom of FeO is the most energetically favorable binding partner for
binding
the Ca atom. energy of thesegeometry
The optimized configurations is −2.32 onto
of FeO adsorption eV, respectively.
the CaO surfaceZhong is shown showed
bond
in lengths
Figure 1. At the of interface,
the FeO the clusters
bond adsorbed
distances ofon CaO(100)
Fe–O and O–Ca areare2.36
2.30ÅÅand
and 1.83 Å, with a
1.90 Å,
energy of 2.58 eV. These values are comparable to those reported by Zhong [
respectively. The binding energy of these configurations is − 2.32 eV, respectively. Zhong
showed
calculatedthat the
Fe–O bond bondlengths of the
length onFeO
theclusters
CaO(100)adsorbed
and on CaO(100)
Ca(110) are 2.36are
surfaces Å and
1.74 Å and
1.83 Å, with a binding energy of 2.58 eV. These values are comparable to those reported by
respectively, which are longer than the Fe–O bond length (1.70 Å) in the free FeO
Zhong [23]. The calculated Fe–O bond length on the CaO(100) and Ca(110) surfaces are
TheÅbinding
1.74 and 1.86 energy of B is −5.91
Å, respectively, which eV. Largethan
are longer negative
the Fe–Obinding energies
bond length (1.70were
Å) inobtaine
Ca(110)
the free FeOsurface
[Link]
The bindingmore energy stable
of B iscomplexes because
−5.91 eV. Large of the
negative low coordination
binding energies o
were obtained
adsorption site. for the Ca(110) surface indicating more stable complexes because of the low
coordination of the top adsorption site.

Figure 1. Top and side views of the optimized structure of FeO on the Ca(100) surface (A) and Ca(110)
Figure(B),where
surface 1. Top and sidered,
yellow, views of the
and blue optimized
balls structure
represent the of FeO
Fe, O, and on the
Ca atoms, Ca(100) surface
(A) an
respectively.
surface (B),where yellow, red, and blue balls represent the Fe, O, and Ca atoms, respective
2.2. Adsorptions of CO and H2 to FeO onto the CaO Surfaces

2.2. Stable adsorption

Adsorptions configurations
of CO and H2 to FeO and the
ontocorresponding adsorption energies of CO
the CaO Surfaces
and H2 to FeO onto the CaO surfaces are shown in Figure 2. In configuration A in Figure 3,
the COStable adsorption
is captured configurations
by the FeO andthe
cluster, breaking theFe–O
corresponding adsorption
bond and forming energies of
a new C–O
H2 to(1.23
bond FeOÅ).ontoThethe
O CaO
of thesurfaces
CO adsorbsare toshown
the Fein Figure
atom (1.972.Å).
In For
configuration
structure B, A
theinCFigure 3
atom can move closer to the O and Fe atoms, forming new C–O
is captured by the FeO cluster, breaking the Fe–O bond and forming a new and C–Fe bonds with C–O bo
bond lengths of 1.91 Å and 1.20 Å, respectively. At the same time, the O–Fe bond is broken
Å). The O of the CO adsorbs to the Fe atom (1.97 Å). For structure B, the C atom c
and the C−O bond length of the CO is stretched to 1.28 Å. Our calculations predict that
closer to the O
configurations andBFeofatoms,
A and forming
the binding neware
energies C–O and
−1.32 eVC–Fe
and −bonds
1.63 eV,with bond lengths o
respectively,
and 1.20
which Å, respectively.
indicates considerable At the same
interaction time, CO
between the and
O–Fe bond
FeO. The is brokenofand
bonding H2 tothe
FeOC−O bon
on the surface of CaO(100) is illustrated in Figure 2C,D. In configuration A,
of the CO is stretched to 1.28 Å. Our calculations predict that configurations A and adsorption of
the H2 molecule leads to a non-negligible change in the FeO geometry, that is, the O–Fe
binding energies are −1.32 eV and −1.63 eV, respectively, which indicates cons
bond of the FeO molecule is broken and the O atom is bound to two H atoms to form H2 O
interaction between CO and FeO. The bonding of H2 to FeO on the surface of CaO
illustrated in Figure 2C,D. In configuration A, adsorption of the H2 molecule leads t
negligible change in the FeO geometry, that is, the O–Fe bond of the FeO molecule i
and the O atom is bound to two H atoms to form H2O compounds. The bond length
Molecules 2023, 28, 5971 4 of 10
Molecules 2023, 28, x FOR PEER REVIEW 4 of 10

compounds. The bond length between H and O, 0.98 Å, is similar to the distance between
twoFor
Å). atoms in a free
structure water
D, the H2 ismolecule (0.96
dissociated andÅ). For structure
adsorbed D,a the
to form newHH–O
2 is dissociated
bond and H–Feand
bond with bond lengths of 0.97 Å and 1.65 Å, respectively. The O–Fe bond is extended Å,
adsorbed to form a new H–O bond and H–Fe bond with bond lengths of 0.97 Å and 1.65 to
respectively.
1.92 The O–Fe
Å. The binding bondofisconfiguration
energies extended to 1.92
C andÅ.DThe
arebinding
−0.74 eVenergies
and −2.03ofeV.
configuration
Figure 2E,F
C and D are −0.74 eV and −2.03 eV. Figure 2E,F shows the binding of CO and H with
shows the binding of CO and H2 with FeO on the CaO(110) surface. In configuration 2E, CO
FeO on the CaO(110) surface. In configuration E, CO molecules are adsorbed to form a
molecules are adsorbed to form a C–O bond (1.36 Å) and C–Fe bond (2.06 Å), in which the
C–O bond (1.36 Å) and C–Fe bond (2.06 Å), in which the adsorption energy is −0.70 eV.
adsorption energy is −0.70 eV. The distance between the O and Fe atoms extended to 2.78 Å
The distance between the O and Fe atoms extended to 2.78 Å and the O–Fe bond is broken.
and the O–Fe bond is broken. The adsorption of H2 to FeO on CaO(110) surface is
The adsorption of H to FeO on CaO(110) surface is illustrated in Figure 2F. H2 adsorbs to
illustrated in Figure22F. H2 adsorbs to FeO, breaking the H–H bond and forming a new
FeO, breaking the H–H bond and forming a new H–O bond (0.97 Å) and a new H–Fe bond
H–O bond (0.97 Å) and a new H–Fe bond (1.75 Å). The binding energy is −1.31 eV.
(1.75 Å). The binding energy is −1.31 eV.

2. Optimized
Figure 2.
Figure Optimizedstructures
structuresofofCO
COand
andHH
2 interaction with FeO the surfaces of CaO(100) (A–D) and
2 interaction with FeO the surfaces of CaO(100) (A–D)

and CaO(110) (E,F), where yellow, red, white, and blue ballsrepresent
CaO(110) (E,F), where yellow, red, white, and blue balls representthe
theFe,
Fe,O,
O,H,
H, and
and Ca atoms,
Ca atoms,
respectively.
respectively.
Molecules 2023, 28,
Molecules 2023, 28, 5971
x FOR PEER REVIEW 55 of 10
of 10

C·s Configuration A C atom of CO C·s Configuration B C atom of CO

C·p C·p

O·s O atom of CO O·s O atom of CO

O·p O·p

Density of States

Density of States
O·s O atom of FeO O·s O atom of FeO
O·p O·p

Fe·s Fe atom of FeO Fe·s Fe atom of FeO

Fe·p Fe·p
Fe·d Fe·d

-5 0 5 -5 0 5
Energy(eV) Energy(eV)

Configuration C C·s Configuration E C atom of CO

H atom of H2
H·s C·p

O·s O atom of CO

Density of States
O·p
Density of States

O atom of FeO O atom of FeO

O·s O·s
O·p O·p

Fe·s Fe atom of FeO

Fe·p
Fe·d

-5 0 5 -5 0 5
Energy(eV) Energy(eV)

Figure 3. PDOS
Figure PDOSofof
adsorption configurations
adsorption A, B,A,C,B,and
configurations C, Eand
in Figure 2. The Fermi
E in Figure 2. Thelevel is located
Fermi at
level is
0 eV. at 0 eV.
located

2.3.
2.3. Partial
Partial Density
Density of
of States
States
The
The adsorption of CO/H
adsorption of onto FeO
CO/H22 onto FeO to to generate
generate surface
surface active
active compounds
compounds isis the
the crucial
crucial
step
step for reduction. Considering the structures of adsorbate and adsorbent, three CO–FeO
for reduction. Considering the structures of adsorbate and adsorbent, three CO–FeO
configurations
configurations (C (C bond
bond toto the
the O
O atom
atom of ofFeO
FeOforming
formingCO CO22 compounds)
compounds) and
and one
oneH H22–FeO
–FeO
configuration
configuration (H bond to the O atom of FeO forming H22O compounds) were explored to
(H bond to the O atom of FeO forming H O compounds) were explored to
investigate
investigate the
the interaction
interaction mechanism.
mechanism. The The partial
partial state
state density
density (PDOS)
(PDOS) of
of configurations
configurations
A,
A, B,
B, C,
C, and
and EE were
were calculated,
calculated, asas shown
shown in inFigure
Figure3.3.
In
In configurations A, B, and D of Figure 3,
configurations A, B, and D of Figure 3, after
after the
the adsorption
adsorption of
of CO
CO onon the
the FeO
FeO
configuration,
configuration, C 2s, C2p, O 2s, and O 2p of FeO shift to lower energies below the Fermi
C 2s, C2p, O 2s, and O 2p of FeO shift to lower energies below the Fermi
energy level and overlap in the range of −5 eV to −0.04 eV, indicating stronger interactions
energy level and overlap in the range of −5 eV to −0.04 eV, indicating stronger interactions
between them. The appearance of these overlapping peaks is related to the formation of the
between them. The appearance of these overlapping peaks is related to the formation of the
CO2 compound. In addition, it is clear that a strong resonance between the Fe 3d orbital
CO2 compound. In addition, it is clear that a strong resonance between the Fe 3d orbital peak
peak and the C 2s and 2p orbital peaks is related to the formation of the C–Fe bond in
and the C 2s and 2p orbital peaks is related to the formation of the C–Fe bond in configuration
configuration B and E. In configuration C, H 1s and O 2p overlap at energies near −1.9 and
B and E. In configuration C, H 1s and O 2p overlap at energies near −1.9 and −1.6 eV,
−1.6 eV, suggesting that s–p hybridization forms covalent bonds. In addition, there are
suggesting that s–p hybridization forms covalent bonds. In addition, there are some resonance
some resonance peaks, which occur at energies above the Fermi level, between the C 2p
peaks, which occur at energies above the Fermi level, between the C 2p and the O 2p for all
and the O 2p for all these configurations, indicating the antibonding interactions between
these configurations, indicating the antibonding interactions between the C atoms and the O
the C atoms and the O atoms. Combining structural analysis and electronic properties, CO
atoms. Combining structural analysis and electronic properties, CO and H2 is chemisorbed
and H2 is chemisorbed on O of FeO.
on O of FeO.
2.4. Charge Transfer
2.4. Charge Transfer
Figure 4 shows that the Löwdin charge analysis of CO molecules or H2 molecules
bondFigure
to FeO4on shows that thesurface.
the Ca(100) Löwdin For charge analysis of A,
configuration COthe molecules
Löwdin or H2 molecules
populations for bond
O(1),
to FeO on the Ca(100) surface.
1.62 4.72 For configuration
0.99
C, Fe, and O(2) are 2s 2p , 2s 2p , 4p 3d 4s , and 2s2.50 0.51A, the
6.58 Löwdin
0.67 populations
1.64 for
4.70 O(1),
2p , respectively, C, Fe,
and O(2)
while are 2s1.62
the atomic 2p4.72, 2s0.99distribution
population 2p2.50, 4p0.513d 6.584s0.67, and 2s1.64 2p4.70, respectively,
before CO adsorption are 2s1.64 2p4.45 , 2swhile the,
1.64 2p2.10

4p 0.66
atomic 6.38 0.51
3d population 1.74
4s , and distribution 4.91 before CO Changes
2s 2p , respectively. adsorption are 2s for
in population 1.642p the
4.45, 3d
2s1.642p2.10,
orbital
4p0.664s
and 3dorbital
6.384s0.51, and 2s1.742p4.91, respectively. Changes in population for the 3d orbital and 4s
of Fe enable the acceptance of electrons after adsorption, which shows that
orbitalare
there of interactions
Fe enable thebetween
acceptance COofandelectrons after For
Fe atoms. adsorption, which A
configuration showsand that there for
similarly are
interactions between CO and Fe atoms. For configuration 0.79
configuration B, the Löwdin population for Fe is 4p 3d 4s , which shows that FeA 6.46
and 0.59
similarly for configuration
B, the Löwdin population for Fe is 4p0.793d6.464s0.59, which shows that Fe accepts electrons
Molecules 2023, 28, x FOR PEER REVIEW 6 of 10

after adsorption. In configuration D in Figure 4, the Löwdin populations for O(1), C, Fe, and
Molecules 2023, 28, 5971 O(2) are 2s1.672p4.68, 2s0.992p2.64, 4p0.863d6.334s0.54, and 2s1.672p4.68, respectively, while the atomic 6 of 10
population distributions before CO adsorption are 2s1.642p4.45, 2s1.642p2.10, 4p0.833d6.304s0.46, and
2s1.732p5.12, respectively. The 4p orbital, 3d orbital, and 4s orbital of Fe accept electrons after
adsorption, while after
accepts electrons the populations
adsorption. In of configuration
the C 2s orbital D inand the 4,
Figure 2pthe
orbital
Löwdin arepopulations
decreased.
Therefore,
for O(1), C, FeOFe,andandCOO(2)
act as
areelectron
2s1.67 2pacceptors
4.68 , 2s0.99and electron
2p2.64 , 4p0.86donors
3d6.33 4sin the
0.54 FeO-CO
, and bond
2s1.67 2p 4.68 ,
system, respectively. The rearrangement of electrons after adsorption
respectively, while the atomic population distributions before CO adsorption are 2s 2p4.45 indicates 1.64that a,
covalent
1.64 bond
2.10 is formed
0.83 6.30 between
0.46 CO and
1.73 FeO.
5.12
2s 2p , 4p 3d 4s , and 2s 2p , respectively. The 4p orbital, 3d orbital, and
For the
4s orbital H2–FeO
of Fe acceptsystem
electrons(configuration
after adsorption, C), the population
while of H and
the populations of OtheisC1s
0.62. The
2s orbital
rearrangement of electrons is due to the transfer of electrons
and the 2p orbital are decreased. Therefore, FeO and CO act as electron acceptorsfrom the H atom to theandO
atom, forming
electron donorstwo H–O
in the [Link]
FeO-CO This system,
chemicalrespectively.
adsorption Theof the O atom by Hof
rearrangement 2 produces
electrons
compounds of H 2O.
after adsorption indicates that a covalent bond is formed between CO and FeO.

Figure
[Link]
Bondingcharge
chargedensity
densityfor
foradsorption
adsorptionconfigurations
configurationsA,
A,B,
B,C,
C,and
andEEin
inFigure
Figure 2.
2.

2.5. Reaction
For thePath of FeOsystem
H2 –FeO and H2 MoleculeC), the population of H and O is 1s0.62 . The
by CO(configuration
rearrangement
The reactionofpath
electrons
of FeOis due
by COto the
andtransfer of electrons
H2 molecule on thefrom the Hsurface
CaO(100) atom tocan
thebe
O
atom, forming two H–O bonds. This chemical adsorption of the O atom by H produces
described as the following process, involving sequential steps: firstly, FeO clusters are
2
compounds
adsorbed of H
on the 2 O.
Ca(100) surface to form new Fe–O bonds and O–Ca bonds (S–FeO+ CO/H2
state) with a binding energy of 2.32 eV (Figure 5). In the process of the reduction of FeO by
2.5. Reaction Path of FeO by CO and H Molecule
CO, the CO molecule is adsorbed to2 generate CO2 compounds (S–FeO–CO state). The
The process
reduction reactionofpath
FeOof FeO bytoCO
is similar theand
onesHreported
2 molecule on the
for the FeOCaO(100)
cluster onsurface can be
the CaO(100).
described as the
Subsequently, Thefollowing
S–FeO–CO process, involving
(IS) needs to crosssequential
through thesteps:
0.63firstly, FeO clusters
eV barrier to S–FeO– are
adsorbed on the Ca(100) surface to form new Fe–O bonds and O–Ca bonds (S–FeO+
CO2(TS), and CO2 gas is then dissociated in an exothermic process (0.40 eV), as shown in2 CO/H
state) with
Figure a binding
6. In the energy
reduction of FeOofby
2.32
H2eV (Figure
(Figure 5). In
5), the O–Fethebond
process of FeO
of the the reduction of FeO
cluster is broken
by CO, the CO molecule is adsorbed to generate CO 2 compounds (S–FeO–CO
and the O atom is bound to two H atoms, crossing the energy barrier of 1.63 eV to experience state). The
reduction process of FeO is similar to the ones reported for the FeO cluster on the CaO(100).
an endothermic process to form the H2O compounds (S–Fe–H2O state). Finally, the H2O
Subsequently, The S–FeO–CO (IS) needs to cross through the 0.63 eV barrier to S–FeO–
compound experiences an endothermic process (0.36 eV) to form the H2O gas (S–Fe+ H2O
CO2 (TS), and CO2 gas is then dissociated in an exothermic process (0.40 eV), as shown
state).
in Figure 6. In the reduction of FeO by H2 (Figure 5), the O–Fe bond of the FeO cluster is
broken and the O atom is bound to two H atoms, crossing the energy barrier of 1.63 eV to
experience an endothermic process to form the H2 O compounds (S–Fe–H2 O state). Finally,
the H2 O compound experiences an endothermic process (0.36 eV) to form the H2 O gas
(S–Fe+ H2 O state).
Comparing the adsorption behavior of two reducing gases with FeO on the CaO(100)
surface, the binding energy of the CO molecule is more negative and H2 needs to cross
through a barrier to absorb FeO. The CO molecule is adsorbed to generate CO2 compounds
in an exothermic reaction. The H2 molecule is adsorbed to generate H2 O compounds in
an endothermic reaction, indicating that the CO molecule is more easily captured than
the H2 molecule. This property is essential for the inertial–collision stage of the reduction.
Secondly, the energy barrier for the CO2 compound’s dissociation from the substrate
indicates the greater difficult posed by dissociation. In the later stage of the reduction,
 Molecules 2023, 28, 5971 7 of 10

the reaction is limited by both interfacial chemical reactions and gas diffusion. H2 has an
advantage at this stage because the product of H2 dissociates from the FeO more easily
than that of CO. In addition, the reduction of iron oxide by CO and H2 is the gas–solid
heterogeneous reaction. Initially, the reactant gas reacts with the external surface and
moves progressively inside incrementally. Compared with CO2 molecules, the smaller
diameter of H2 O molecules enhances diffusion and separation towards the interior of iron
oxide, thereby accelerating the reaction. Our results reveal that the reduction of FeO by H2
is controlled by adsorption steps. High temperature has a positive effect on the adsorption
of H2 . In addition, the separation of CO2 and H2 O from the reaction interface leads to the
Molecules
Molecules2023,
2023,28,
28,xxFOR
FORPEER
conversion from FeO to metallic iron, which is the final step of the iron oxide reduction
PEERREVIEW
REVIEW 77 ofof 10
10
reaction. CaO promotes the reduction of FeO into Fe by H2 at high temperatures, and then
metallic iron accumulates to form iron whiskers.
00
S+FeO+CO
S+FeO+CO
S+FeO+H
S+FeO+H
22 Configuration
ConfigurationAA
TS
TS Configuration
ConfigurationCC
-1-1

ISIS
-2-2
-- -1.44
(ev)

-1.44eVeV
Energy (ev)

S SFeO+H
FeO+H2
2
S- -FeO+CO -0.74
SFeO+CO -0.74eVeV --
Energy

S SFe+H
Fe+H2O
2O
TS
TS
-3-3 0.36
0.36eV
eV
-- --
FeOHH
S SFeO 22
--
S SFe+CO
FSFS Fe+CO2 2
-1.31
-1.31eVeV ISIS --0.63
0.63eV
eV
FS
FS 0.23
0.23eV
eV
-- --
S SFeO
FeOCOCO
-4-4

-5-5
Reaction
Reactionpath
path
Figure
Figure5.5.5.
Figure Calculated
Calculated
Calculated energy
energy
energyprofiles
profiles for
forthe
profiles thereduction
forreduction path
pathofofpath
the reduction FeO
FeObybyCO
of COand
FeO byHH
and 2 2on
CO CaO(100)
onand H2 onsurface.
CaO(100) surface.S-S-
CaO(100)
FeO
FeO + CO/H
+ CO/H
surface. S-FeO2 : state
2: state of
+ CO/H FeO
of FeO cluster
clusteris adsorbed
is adsorbed on the Ca(100)
onadsorbed
the Ca(100) surface
on surface and free
and surface CO/H
free CO/H molecule;
and2 molecule;
2 S-S-2
2 : state of FeO cluster is the Ca(100) free CO/H
FeO-CO/H
FeO-CO/H 2:2:state
stateofofCO/H
CO/H 2 2is
isadsorbed
adsorbed byby the
theFeO;
FeO;S-Fe-CO
S-Fe-CO 2/H
2/H2O:
2O:state
stateofofCOCO 2/H
2/H2O
2Ocompounds
compounds
molecule; S-FeO-CO/H 2 : state of CO/H 2 is adsorbed by the FeO; S-Fe-CO 2 /H 2 O: state of CO 2 /H 2O
generated;
generated; S-Fe ++CO CO2/H 2O:
2O:state of dissociation of CO
CO2/H 2O
2Ogas.
compoundsS-Fe generated; 2/H
S-Fe state
+ COof/Hdissociation
O: state ofofdissociation
2 2
2/H gas.
of CO /H O gas. 2 2

Figure 6. Top views of the optimized CaO surfaces: (A) CaO(100) surface; (B) CaO(110) surface,
Figure
[Link]
Topviews
viewsofofthe
theoptimized
optimizedCaO
CaOsurfaces:
surfaces:(A)
(A)CaO(100)
CaO(100)surface;
surface;(B)
(B)CaO(110)
CaO(110)surface,
surface,where
where
where the blue ball represents the Ca atom and the red ball represents the O atom.
the
theblue
blueball
ballrepresents
representsthetheCa
Caatom
atomand
andthe
thered
redball
ballrepresents
representsthe
theOOatom.
atom.
3. Materials and Methods
Comparing
Comparing the
theadsorption
adsorption behavior
behavior of
oftwo
two reducing
reducinggasesgaseswithwith FeO
FeOon onthe CaO(100)
theESPRESSO
CaO(100)
Our first principles calculations were performed using the Quantum
surface,
surface, the binding energy of the CO molecule is more negative and H 2 needsto
needs tocross
package,the bindingtheenergy of the CO molecule is more negative and Htheory cross
2
adopting spin–polarized plane-wave density functional [28]. The
through
through aabarrier
barrier to
toabsorb
absorb FeO.
FeO. The
The CO
CO molecule
molecule isisadsorbed
adsorbed totogenerate
generate COCO 2 compounds
2 compounds
electronic structure was modeled by Generalized Gradient Approximation (GGA) with
in
inan
anexothermic
exothermicreaction.
[Link]
TheHH2 2molecule
moleculeisisadsorbed
adsorbedtotogenerate
generateHH2O 2Ocompounds
compoundsin inan
an
endothermic
endothermicreaction,
reaction,indicating
indicatingthat thatthe
theCOCOmolecule
moleculeisismoremoreeasily
easilycaptured
capturedthan thanthe
theHH2 2
molecule.
[Link]
Thisproperty
propertyisisessential
essentialforforthe
theinertial–collision
inertial–collisionstagestageof ofthe
thereduction.
[Link],
Secondly,
the energy barrier for the CO
the energy barrier for the CO2 compound’s dissociation from the substrate indicatesthe
2 compound’s dissociation from the substrate indicates the
greater
greaterdifficult
difficultposed
posedbybydissociation.
[Link] Inthe
thelater
laterstage
stageof
ofthe
thereduction,
reduction,the thereaction
reactionisis
Molecules 2023, 28, 5971 8 of 10

the Perdew–Burke–Ernzerhof (PBE) functional. Projector Augmented Wave (PAW) was

employed to represent the interactions between the electrons and the ions. The cutoff
energy was 50 Ry for the wavefunction and 500 Ry for the charge density [29]. The
4 × 4 × 1 Monkhorst–Pack grid was used for sampling the Brillouin zone. In order to
realize the effect of the 3d state of Fe [30], the GGA + U method with U = 4.2 eV was used
in all adsorption configurations [31,32]. For the FeO cluster, CO, and H2 optimization, the
periodic slabs were decoupled using a vacuum layer (15 Å) to relax. The Ca(100) surface
and the Ca(110) surface were modeled using periodic slabs of about five atomic layers with
a 2 × 2 supercell, as shown in Figure 6. During optimization, the atoms in the bottom three
layers of the CaO(100) surface and the CaO(110) surface were fixed, whereas the other
layers and adsorbates were allowed to relax. The periodic slabs were decoupled using a
vacuum layer (15 Å) to eliminate interaction between two adjacent slabs. The three bottom
CaO(100) layers were fixed during relaxation. The optimized Ca–O bond length between
the top two layers was 2.33 Å, which is approximately smaller than the experimental value
of about 0.01%. Both configurations resulted in negligible changes in the geometry of the
CaO(100) surface. The configuration of the fixed bottom three layers was reliable.
The following formula was used to calculate the adsorption energy of all possible
configurations:
Ead = Esys − Esurf − Emol (1)
where Esys , Emol , and Esurf are the energy of the system, the isolated molecule, and the
clean surface, respectively. All the computations were performed using the GPC su-
percomputer at the SciNet HPC Consortium on the Compute/Calcul Canada national
computing platform.

4. Conclusions
The adsorption behaviors of CO and H2 to FeO onto the CaO surfaces have been
determined using density functional theory to study the reactions of FeO with CO and H2 .
For the adsorption of FeO onto CaO surfaces, the energy of the adsorption of FeO onto
the CaO(110) surface is higher than that onto the CaO(100) surface. After CO adsorption,
CO bonds to the O atom of FeO, forming CO2 compounds in both configurations through
the C atom. In the adsorption of H2 , the H2 adsorbs to FeO, breaking the H–H bond and
forming a new H–O bond and a new H–Fe bond. In addition, H2 favors the O atom of FeO,
forming an H2 O compound on CaO surfaces and the Fe–O bond is broken.
Our results reveal the competitive adsorption behavior of FeO by CO and H2 on the
CaO surface. The CO molecule is adsorbed to generate CO2 compounds in an exothermic
reaction. The H2 molecule is adsorbed to generate H2 O compounds in an endothermic
reaction. The results indicate that CO is more easily and stably adsorbed on the FeO
than H2 , which is essential for the inertial-collision stage of the reduction. However, the
dissociation energy of the CO2 compound from the reaction interface will overcome a
higher energy barrier than that of H2 O. In the later stage of the reduction, the reaction is
limited by both interfacial chemical reactions and gas diffusion. H2 has an advantage at
this stage. Therefore, the reduction of FeO by H2 is controlled by adsorption steps. High
temperature has a positive effect on the adsorption of H2 . In addition, the separation of
CO2 and H2 O from the reaction interface leads to the conversion from FeO to metallic iron,
which is the final step of the iron oxide reduction reaction. CaO promotes the reduction of
FeO into Fe by H2 at high temperatures, and then metallic iron accumulates to form iron
whiskers. Sticking can easily occur in the high temperature ironmaking reduction of fine
iron ore, thereby decreasing the reduction efficiency.

Author Contributions: Formal analysis, Y.L.; Investigation, W.Y.; Discussion and modification of the
manuscript, K.L.; Data curation, Y.D. and P.S.; Writing—original draft, Z.W.; Project administration,
Z.W. All authors have read and agreed to the published version of the manuscript.
Molecules 2023, 28, 5971 9 of 10

Funding: This research was funded by the Innovation Capacity Enhancement Project of XingTai
(2022zz113), the Science and Technology Project of Hebei Education Department (QN2023192).
Data Availability Statement: The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Acknowledgments: The authors acknowledge the technical support of Bo Zhao of the University of
Science and Technology Beijing. And my warm gratitude also goes to my family (Wang P.J., Chen
R.Q.) who gave me much encouragement and financial support respectively.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Not applicable.

References
1. Zieliński, J.; Zglinicka, I.; Znak, L.; Kaszkur, Z. Reduction of Fe2 O3 with hydrogen. Appl. Catal. A Gen. 2010, 381, 191–196.
[CrossRef]
2. LMurr, E.; Foltz, J.V. Gaseous reduction of Fe2 O3 compacts at 600 to 1050 ◦ C. J. Mater. Sci. 1986, 21, 3889–3900.
3. Saharuddin, T.S.T.; Samsuri, A.; Salleh, F.; Othaman, R.; Kassim, M.B.; Hisham, M.W.M.; Yarmo, M.A. Studies on reduction of
chromium doped iron oxide catalyst using hydrogen and various concentration of carbon monoxide. Int. J. Hydrogen Energy 2017,
42, 9077–9086. [CrossRef]
4. Sastri, M.V.C.; Viswanath, R.P.; Viswanathan, B. Studies on the reduction of iron oxide with hydrogen. Int. J. Hydrogen Energy
1982, 7, 951–955. [CrossRef]
5. Yi, L.; Huang, Z.; Jiang, T. Sticking of iron ore pellets during reduction with hydrogen and carbon monoxide mixtures: Behavior
and mechanism. Powder Technol. 2013, 235, 191–196. [CrossRef]
6. Vinters, E.T.T.V. Gaseous reduction of iron oxides: Part I. Reduction of hematite in hydrogen. Metall. Mater. Trans. B 1971, 2,
3175–3188.
7. Lin, H.Y.; Chen, Y.W.; Li, C. The mechanism of reduction of iron oxide by hydrogen. Thermochim. Acta 2003, 400, 61–67. [CrossRef]
8. Hou, B.; Zhang, H.; Li, H.; Zhu, Q. Study on Kinetics of Iron Oxide Reduction by Hydrogen. Chin. J. Chem. Eng. 2012, 20, 10–17.
[CrossRef]
9. Bahgat, M.; Khedr, M.H. Reduction kinetics, magnetic behavior and morphological changes during reduction of magnetite single
crystal. Mater. Sci. Eng. B 2007, 138, 251–258. [CrossRef]
10. Chen, H.; Zheng, Z.; Chen, Z. Multistep reduction kinetics of fine iron ore with carbon monoxide in a micro fluidized bed reaction
analyzer. Metall. Mater. Trans. B 2017, 48, 841–852. [CrossRef]
11. Bonalde, A.; Henriquez, A.; Manrique, M. Kinetic analysis of the iron oxide reduction using hydrogen-carbon monoxide mixtures
as reducing agent. ISIJ Int. 2005, 45, 1255–1260. [CrossRef]
12. Kim, W.-H.; Lee, S.; Kim, S.-M.; Min, D.-J. The retardation kinetics of magnetite reduction using H2 and H2 –H2 O mixtures. Int. J.
Hydrogen Energy 2013, 38, 4194–4200. [CrossRef]
13. Jozwiak, W.; Kaczmarek, E.; Maniecki, T.; Ignaczak, W.; Maniukiewicz, W. Reduction behavior of iron oxides in hydrogen and
carbon monoxide atmospheres. Appl. Catal. A Gen. 2007, 326, 17–27. [CrossRef]
14. Zhao, Z.; Tang, H.; Guo, Z. Micro behavior of the precipitation of metallic Fe in the reduction of Fe2 O3 under CO Atmosphere. J.
Iron Steel Res. 2012, 24, 26–28.
15. Corbari, R.; Fruehan, R. Reduction of iron oxide fines to wustite with CO/CO2 gas of low reducing potential. Metall. Mater. Trans.
B 2010, 41, 318–329. [CrossRef]
16. Zhong, H.; Wen, L.; Li, J.; Xu, J.; Hu, M.; Yang, Z. The adsorption behaviors of CO and H2 on FeO surface: A density functional
theory study. Powder Technol. 2016, 303, 100–108. [CrossRef]
17. Umadevi, T.; Sah, R.; Mahapatra, P. Influence of sinter basicity (CaO/SiO2 ) on low and high alumina iron ore sinter quality. Miner.
Process. Extr. Metall. 2014, 123, 75–85. [CrossRef]
18. Zhong, Y.; Wang, Z.; Guo, Z.; Tang, Q. Prevention of agglomeration/defluidization in fluidized bed reduction of Fe2 O3 by CO:
The role of magnesium and calcium oxide. Powder Technol. 2013, 241, 142–148. [CrossRef]
19. Hayashi, S.; Iguchi, Y. Factors affecting the sticking of fine iron ores during fluidized bed reduction. ISIJ Int. 1992, 32, 962–971.
[CrossRef]
20. Komatina, M.; Gudenau, H.W. The sticking problem during direct reduction of fine iron ore in the fluidized bed. Metall. Mater.
Eng. 2004, 10, 309–328. [CrossRef] [PubMed]
21. Zhao, Z.-L.; Tang, H.-Q.; Guo, Z.-C. Effects of CaO on precipitation morphology of metallic iron in reduction of iron oxides under
CO atmosphere. J. Iron Steel Res. Int. 2013, 20, 16–24. [CrossRef]
22. Geva, S.; Farren, M.; John, D.S.; Hayes, P. The effects of impurity elements on the reduction of wustite and magnetite to iron in
CO/CO2 and H2 /H2 O gas mixtures. Metall. Trans. B 1990, 21, 743–751. [CrossRef]
23. Zhong, H.; Er, D.; Wen, L. Theoretical study on influence of CaO and MgO on the reduction of FeO by CO. Appl. Surf. Sci. 2017,
399, 630–637. [CrossRef]
Molecules 2023, 28, 5971 10 of 10

24. Dong, C.; Sheng, S.; Qin, W.; Lu, Q.; Zhao, Y.; Wang, X.; Zhang, J. Density functional theory study on activity of α-Fe2 O3 in
chemical-looping combustion system. Appl. Surf. Sci. 2011, 257, 8647–8652. [CrossRef]
25. Sun, X.; Kurahashi, M.; Pratt, A.; Yamauchi, Y. First-principles study of atomic hydrogen adsorption on Fe3 O4 (100). Surf. Sci.
2011, 605, 1067–1073. [CrossRef]
26. Qin, W.; Chen, Q.; Wang, Y.; Dong, C.; Zhang, J.; Li, W.; Yang, Y. Theoretical study of oxidation–reduction reaction of Fe2 O3
supported on MgO during chemical looping combustion. Appl. Surf. Sci. 2013, 266, 350–354. [CrossRef]
27. Lin, C.; Qin, W.; Dong, C. Reduction effect of α-Fe2O3 on carbon deposition and CO oxidation during chemical-looping
combustion. Chem. Eng. J. 2016, 301, 257–265. [CrossRef]
28. Giannozzi, P.; Baroni, S.; Bonini, N.; Calandra, M.; Car, R.; Cavazzoni, C.; Ceresoli, D.; Chiarotti, G.L.; Cococcioni, M.; Dabo, I.
QUANTUM ESPRESSO: A modular and open-source software project for quantum simulations of materials. J. Phys. Condens.
Matter 2009, 21, 395502. [CrossRef] [PubMed]
29. Nguyen, M.T.; Seriani, N.; Gebauer, R. Water adsorption and dissociation on α-Fe2 O3 (0001): PBE+ U calculations. J. Chem. Phys.
2013, 138, 194709. [CrossRef] [PubMed]
30. Cococcioni, M.; De Gironcoli, S. Linear response approach to the calculation of the effective interaction parameters in the LDA+ U
method. Phys. Rev. B 2005, 71, 035105. [CrossRef]
31. Rödl, C.; Fuchs, F.; Furthmüller, J.; Bechstedt, F. Quasiparticle band structures of the antiferromagnetic transition-metal oxides
MnO, FeO, CoO, and NiO. Phys. Rev. B 2009, 79, 235114. [CrossRef]
32. Eom, T.; Lim, H.-K.; Goddard, W.A.; Kim, H. First-principles study of iron oxide polytypes: Comparison of GGA+ U and hybrid
functional method. J. Phys. Chem. C 2015, 119, 556–562. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.