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Effective hydrogen production from propane steam reforming over bimetallic

co-doped NiFe/Al2O3 catalyst

Article · November 2016

DOI: 10.1016/j.jiec.2016.10.046

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 Journal of Industrial and Engineering Chemistry 46 (2017) 324–336

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Effective hydrogen production from propane steam reforming over

bimetallic co-doped NiFe/Al2O3 catalyst
Kang Min Kima , Byeong Sub Kwaka , No-Kuk Parkb , Tae Jin Leeb , Sang Tae Leec,
Misook Kanga,*
a
Department of Chemistry, College of Science, Yeungnam University, Gyeongsan, Gyeongbuk 38541, Republic of Korea
b
School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeongbuk 38541, Republic of Korea
c
Wooshin Com., Gyeongsan, Gyeongbuk 38470, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history:
Received 3 September 2016 In this study, we investigated the role of Fe oxide as a promoter to improve the redox properties of Ni in
Received in revised form 18 October 2016 PSR (propane steam reforming), thereby extending its lifetime and enabling it to be more easily oxidized
Accepted 29 October 2016 by the CO generated to produce CO2. Bimetallic NiFe supported on g-Al2O3 (30NixFeyO/70Al2O3) samples
Available online 8 November 2016 are prepared as catalysts and characterized by XRD, TEM, H2-TPR, TPO, and XPS. Moreover, a mechanism
for propane steam reforming over the 30NixFeyO/70Al2O3 catalyst is proposed on the basis of the GC and
Keywords: mass spectroscopy results and CO-, C3H8-, and H2O-temperature programmed desorption analysis.
Propane steam reforming Consequently, the Fe components in the 30NixFeyO/70Al2O3 catalysts suppressed the agglomeration
Hydrogen production
between the Ni and Al particles. The catalytic performances on the 30NixFeyO/70Al2O3 catalysts are
Fe-promoter
improved by the reduced deposition of carbon compared to that on the 30NiO/70Al2O3 one: at 700
C, the
30NixFeyO/70Al2O3
Particle agglomeration hydrogen selectivity amounted to 86% in the 30Ni0.8Fe0.2O/70Al2O3 catalyst compared to 79% in the
30NiO/70Al2O3 one.
ã 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction compressible to a transportable liquid. Thus, propane is a potential

Hydrogen has attracted interest as an efficient and environmen-
tally friendly energy carrier. The methods of hydrogen production
include water electrolysis [1], the partial oxidation or gasification of
heavy oil or coal [2], and steam reforming of hydrocarbons [3]. It
should be noted however that from an economic viewpoint, the
steam reforming of hydrocarbons has been highlighted as one of the
most reasonable methods of producing hydrogen. Currently, the
hydrocarbons used as the hydrogen sources in the steam reforming
reaction can be separated into two kinds: firstly, light paraffins such
as methane [4], ethane [5], propane [6] and butane [7], and secondly,
oxidized compounds such as methanol [8], dimethylether [9],
ethanol [10] and acetic acid [11]. In particular, propane has many
advantages as a hydrogen source candidate; it is a gas at standard
temperature and pressure and a by-product of natural gas processing
and petroleum refining, is commonly used as a fuel for engines, oxy-
gas torches, portable stoves and residential central heating, but is
* Corresponding author. Fax: +82 53 815 5412.
E-mail address: mskang@ynu.ac.kr (M. Kang).
candidate as a hydrogen carrier, because of its common storage (LP
gases) and existing widely spread infrastructure. Additionally,
propane steam reforming (PSR) is the most economical pathway
in terms of the hydrogen yield, since hydrogen is produced from
steam as well as propane, as shown in the following equation for
propane overall steam reforming:
C3H8 + 6H2O ! 3CO2 + 10H2 DH
298 = 499 kJ/mol (1)
Since industrial operations always use excess steam to
minimize catalyst deactivation, the maximum yield of hydrogen
per mole of propane fed can reach 10.
In practice, PSR is performed at high temperatures over Ni-
based catalysts. However, the high temperature required may favor
several routes to the formation of carbon deposits and the
decomposition of the hydrocarbons. In addition, Ni catalysts tend
to agglomerate and then lose their active surface area under PSR
conditions, resulting in short catalyst lifetimes. Consequently,
novel preparation and promotion techniques that can resist rapid
catalyst deactivation by coking and sintering are essential. Much of
this research effort has focused on developing Ni catalysts with
improved resistance to coke formation by adding promoters. Alkali

http://dx.doi.org/10.1016/j.jiec.2016.10.046
1226-086X/ã 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336
metals, such as K2O [12] and MgO [13], have been shown to
improve the coking resistance by enhancing the carbon gasifica-
tion, but at the cost of reduced catalytic activity. The effects of
novel metals, such as Pt, Rh and Ru, have also been investigated
[14–16], and their introduction into Ni-based catalysts to increase
their hydrogen selectivity and decrease their coke deposition
showed dramatic results. More recently, bi or tri metallic catalytic
species have been investigated. Laosiripojana et al. [17] reported
that adding CeO2 to Ni/Al2O3 catalysts enhanced the nickel
dispersion and reactivity of the carbon deposits, leading to
improved catalytic activity and stability in the steam reforming
of propane. Althenayan et al. [18] researched the use of bimetallic
Co–Ni/Al2O3 catalysts for propane dry reforming, in order to
determine the intrinsic reaction rate simultaneously with the
carbon-induced deactivation coefficient from the transient rate
data over an extended period of time (up to 72 h), for propane dry
reforming over a Co–Ni catalyst at 823–973 K. Malaibari et al. [19]
also investigated the effect of Mo as a promoter in alumina-
supported Ni catalysts for PSR at 450
C. Mo promotion showed a
beneficial effect by both decreasing the rate of carbon deposition
and increasing the catalytic activity.
In order to develop more durable and cheaper catalysts for use
in PSR, this study broke new ground. Fe oxide was introduced as a
promoter to improve the redox properties of Ni, thereby extending
its lifetime and enabling it to be more easily oxidized by the CO
generated to produce CO2. Iron oxide can be thermally reduced by
CO during PSR as follows: Fe2O3 + 3CO ! 2Fe + 3CO2. Additionally,
partial reduction with hydrogen at about 400
C gives magnetite, a
black magnetic material that contains both Fe(III) and Fe(II)
through the reaction: 3Fe2O3 + H2 $ 2Fe3O4 + H2O and this reaction
can occur reversely also. Thus, in this study, we attempted to apply
bimetallic NiFe catalysts supported on g-Al2O3 to PSR. The
prepared catalysts were characterized by XRD, TEM, H2O-, C3H8-
and CO-TPD, H2-TPR, TPO, and XPS. In addition, the nature of the
promoter action afforded by Fe oxide was examined. The results
were applied to the design of practical catalysts for PSR.
Experimental
Preparations of the 30NixFeyO/70Al2O3 catalysts
The bimetallic NiFe catalysts supported on g-Al2O3 (30NixFeyO/
70Al2O3) were prepared using impregnation methods [20] with a
Ni-based catalyst content of 30 wt.% and Fe/Ni atomic ratios of 0,
0.1, 0.25, and 0.43. The 70 wt.% g-Al2O3 (Junsei Co., Japan) was
mixed in ethanol solvent at room temperature and the suspension
was stirred for 1 h. Then, NiCl2 (99.99%, Junsei Co., Japan) and FeCl2
(99.99%, Junsei Co., Japan) as the Ni and Fe sources, respectively,
were added to the suspension containing 70 wt.% g-Al2O3 powder,
and the mixture was stirred at 40
C. At this time, the catalysts
were labeled NixFey, where x and y indicate the atomic %. The
NixFey main catalytic species were loaded onto the external
surfaces of alumina and the total loaded weights in all of the
samples were the same, viz. 30 wt.%. After aging for 3 h, the final
solutions were evaporated at 70
C for 6 h and dried at 50
C for
24 h in an oven. The final samples were treated thermally at 800
C
for 3 h in air, and reduced by H2/argon (1:10 ratio) at 700
C for 2 h
to generate the NiFe oxide composites. The following four
experimental bimetallic NiFe catalysts supported on Al2O3 were
prepared for comparison: 30NiO/70Al2O3, 30Ni0.9Fe0.1O/70Al2O3,
30Ni0.8Fe0.2O/70Al2O3, and 30Ni0.7Fe0.3O/70Al2O3.
Physical properties of the 30NixFeyO/70Al2O3 catalysts
The 30NiO/70Al2O3 and 30NixFeyO/70Al2O3 catalysts were
examined by powder XRD (model MPD from PANalytical) using
325
nickel-filtered CuKa radiation (30.0 kV, 30.0 mA) over the 2u range
of 10–100
. The core and shell shapes of the catalyst particles were
determined by high-resolution TEM (H-7600, Hitachi, Japan)
operated at 120 kV. The BET (Brunauer, Emmett and Teller) surface
areas of the catalysts were measured using a Belsorp II instrument.
The BET surface measurement was performed by nitrogen gas
adsorption using a continuous flow method with a mixture of
nitrogen and helium as the carrier gas. A tube was filled with 0.2 g
of the sample under an N2 atmosphere and then out-gassed for 1 h
at 200
C before the measurements. After pre-treatment, the
samples were cooled down to room temperature and then exposed
to liquid nitrogen for 2 h. In the a-plot method, the adsorption
volume, Vads (p/p0), which was normalized to Vads for the reference
material, is used as a new x-axis to plot the adsorption isotherms
for the samples of interest. The discrete adsorption data for the
reference material was interpolated numerically to generate a
continuous x-axis. The XPS (AXIS-NOVA Kratos Inc.) spectroscopy
measurements of Ni2p, Fe2p Al2p, O1s, and C1s using a non-
monochromatic AlKa (1486.6 eV) X-ray source were performed at
the Yeungnam University instrumental center, Korea. The powders
were pelletized at 1.2  104 kPa for 1 min and the 1.0-mm pellets
were stored overnight in a vacuum (1.0  107 Pa) to remove the
water molecules from the surface before the measurements. The
base pressure in the system was less than 1 109 Pa. The
experiments were performed using a 200-W source power and
an angular acceptance of 5
. The analyzer axis formed a 90
angle
with the specimen surface. The Shirley function was used to
subtract the background for the XPS data analysis. The signals were
fitted using the mixed Lorentzian–Gaussian curves.
Gas adsorption abilities of the 30NixFeyO/70Al2O3 catalysts
The H2-TPR experiments for the as-synthesized 30NixFeyO/
70Al2O3 samples were conducted using the same equipment as
that used for the thermo-gravimetric analysis (TGA) experiment
(Shinco com., Korea). Approximately 0.05 g of the catalyst was
pre-treated under flowing argon gas (30 mL min1) at 300
C for
1 h and then cooled to 50
C. The analysis was carried out by
increasing the catalyst temperature from room temperature to
900
C at a rate of 5
C min1 under H2 (5 vol.%)/Ar with a flow rate
of 50 mL min1.
The adsorption abilities of the catalysts for the CO and C3H8
gases were measured from the CO- and C3H8-TPD experiments
performed using a BELCAT (Bel Japan Inc., Japan). Each catalyst
(0.05 g) was placed in the quartz reactor of the TPD apparatus. The
catalysts were pretreated at 300
C for 1 h under a He flow
(30 mL min1) to remove the physically absorbed water and
impurities. CO (5 vol.% CO/He) and C3H8 (25 vol.% C3H8/He) gases
were injected into the reactor for 1 h at a rate of 50 mL min1 at
50
C. The physically absorbed CO and C3H8 gases were removed by
evacuating the catalyst samples at 50
C for 30 min. The furnace
temperature was increased from 50 to 900
C at a rate of
10
C min1 under He flow. The desorbed CO and C3H8 gases were
detected using a TCD detector.
The activation energy for water desorption in the catalysts was
determined by a TGA apparatus equipped with a micro thermo-
differential and gravimetric analyzer (Shinco com., Korea). The
samples were analyzed after coming into contact with saturated
(NH4)2SO4 for 24 h to maintain identical water vapor conditions.
Blaine and Kissinger [21] presented a useful equation to calculate
the activation energies of various thermal reactions based on the
shifts of the maximum deflection temperature of the DTA
thermograms upon the changing of the heat rates, as follows.
The Kissinger equation was selected and is given as ln(C/Tm2) =
Ea/RTm + a constant, where C is the DTA heating rate (
C/min),
Tm is the crystallization peak temperature, Ea is the activation
326 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336
energy required for crystallization and R is the gas constant
(1.987 cal/mol).
Propane steam reforming (PSR) reaction on the 30NixFeyO/70Al2O3
catalysts
The reactor for PSR in this study was designed as a fixed bed-
type [22], and the devices that were employed are shown in Fig. 1:
it consists of a feed gas (C3H8) supply, a water supply, a quartz
reactor, and analysis equipment (GC). The catalytic activities were
measured at 700
C for a reaction time of 10 h at a steam-to-
propane ratio of 1:6 (mol.%) with a GHSV (gas hourly space
velocity) of 6000 h1. The catalyst (0.4 g) was pelletized to a 20–
24 mesh and then packed with a small amount of quartz wool to
prevent the catalyst from moving in the fixed-bed quartz reactor,
which was then mounted vertically inside the furnace. All of the
catalysts were reduced in situ under hydrogen (10 mL min1) for
2 h at 700
C before each run. In this study, the amount of steam
was adjusted by regulating the temperature according to the
partial pressure law [23]. The flow rate was kept constant at
10.0 mL/min for propane gas (25.0 vol.%). Argon gas was used to
carry the vaporized mixture into the reactor. The samples were
pre-reduced by H2 (5 vol.%)/Ar gases at 700
C for 2 h before the
reaction. The reaction products during PSR were measured by an
on-line gas chromatograph (Donam DS6200, Donam Company,
Korea) equipped with a thermal conductivity detector (TCD) and
flame ionizing detector (FID). H2, CO, CO2, CH3CHO, CH3COCH3, and
CH3COOH were detected using the TCD, whereas the FID was used
to detect CH4, C2H4, C2H6, C3H8, and the other products.
Additionally, mass spectroscopy (BelMass, Bel Japan Inc., Japan)
was used to confirm the intermediates evolved during PSR. The
C3H8 conversion and CH4, CO2, CO, and H2 selectivities were
defined as:
C3H8 conversion (%) = ([C3H8]in  [C3H8]out)/[C3H8]in  100,
H2 (CO, CO2, or CH4) selectivity (%) = [H2 (CO, CO2, or CH4)]out/
([CO2 + CO + CH4 + H2]out  100. (3)
Fig. 1. Equipment configuration of batch bed type reactor for propane steam reforming.
Results and discussion
Characteristics of the 30NixFeyO/70Al2O3 catalysts
Based on the mechanism of the hydrocarbon reforming
reaction, it was confirmed that its rate increases in the presence
of metallic gradients [24]. Therefore, many studies have examined
the reforming reaction after reducing the catalysts. The catalytic
reduction temperature is also very important, and the activity of
the catalyst is dependent on the reduction temperature. Therefore,
to determine the proper pre-reduction temperature for the
samples before PSR, the changes corresponding to the reduction
of the Ni and Fe components were observed in the H2-TPR profiles
of all of the fresh samples, as shown in Fig. 2. Generally, in H2-TPR,
the peak area corresponds to the hydrogen uptake and the peak
location depends on how easily the catalyst species are reduced
[25]. The peak locations for the three 30NixFeyO/70Al2O3 catalysts
were almost the same, but the amounts of Ni reduced in them
decreased in proportion to the amount of Fe added. The NiO
isolated from the 30NiO/70Al2O3 and 30NixFeyO/70Al2O3 samples
was considered to be reduced to metallic Ni [26] at approximately
380–550
C, and the peaks were separated into two curves,
corresponding to slightly different oxidation states. Another
sharper and larger Ni-reduction curve was exhibited at higher
temperatures in the range of 700–900
C in both the 30Ni/70Al2O3
and 30NixFeyO/70Al2O3 samples, which corresponds to the
reduction of NiO to Ni in the spinel structured NiAl2O4, and the
peak location was shifted to a slightly higher temperature in
30NixFeyO/70Al2O3 compared to that in 30NiO/70Al2O3. This
appears to be due to the influence of the added iron. Furthermore,
there are three types of reduction curves at around 350, 500, and
750
C, respectively, on 30FeO/70Al2O3, which correspond to the
reductions of the Fe oxide in its various oxidation states and, in
particular, the isolated Fe components were reduced at higher
(2)
temperature compared to the Ni components. The temperature to
reduce the exposed NiO and FeO ingredients were kept at 700
C
before PSR. It is expected that some of the oxidized Ni or Fe
components might remain after PSR, which would affect their
catalytic activity.
 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336 327

Fig. 2. H2-TPR profiles of the three fresh samples, 30NiO/70Al2O3, 30FeO/7070Al2O3 and 30Ni0.8Fe0.2O/70Al2O3.

The crystallinities of the synthesized samples before (A) and
after (B) hydrogen pre-treatment were examined by XRD, as shown
in Fig. 3. In the hydrogen pre-treated samples (Fig. 3A), the main
XRD peaks for the 30NiO/70Al2O3 samples were observed at
2u = 37.25
(111), 43.28
(200), 63.88
(220), 75.42
(311), 79.41

(222), and 95.58
(400), which correspond to cubic crystalline NiO
[27]. Special peaks for spinal structured NiAl2O4 [JSPDS no. 01-078-
1601, Fd-3m, Cubic] and FeAl2O4 [JSPDS no. 00-003-0894, Fd-3m,
Cubic] were observed in all of the 30NixFeyO/70Al2O3 samples,
however, there were no peaks for NiO or FeO, which means that the
Ni and Fe components are very well dispersed over the surface of
Al2O3, causing them to have a perfect spinel structure. Generally,
the crystallite size decreases with increasing line-broadening of
the peaks. The crystallite size was estimated using Scherrer’s
equation [28], t = 0.9l/bcos u, where l is the wavelength of the
incident X-rays, b is the full width at half maximum height in
radians, and u is the diffraction angle in radians. The estimated
crystallite sizes based on the (111) and (311) planes of the NiO and
NiAl2O4 formed in the 30NiO/70Al2O3, 30Ni0.9Fe0.1O/70Al2O3,
30Ni0.8Fe0.2O/70 Al2O3, and 30Ni0.7Fe0.3O/70Al2O3 samples were
9.04, 7.29, 9.21, and 17.4 nm, respectively. Consequently, the
crystallites sizes decreased with increasing amount of Fe added.
On the other hand, Fig. 3B shows the XRD patterns after the
hydrogen pre-treatment. The main XRD peaks for metallic cubic
crystalline Ni [JSPDS no. 01-1258, Fm-3m] after reduction in all of
the samples were observed at 2u = 44.37
(111), 51.60
(200), 76.08

(220), and 92.09
(311). Small peaks, which were assigned to spinel
structured NiAl2O4, were also observed in all of the reduced
samples, which means that the Ni and Fe components are well
combined with the Al2O3 support ingredients. The estimated
crystallite sizes based on the (111) plane of the formed Ni were
compared, and the values were 20.12, 23.76, 24.92, and 25.82 nm,
respectively, in the 30NiO/70Al2O3, 30Ni0.9Fe0.1O/70Al2O3,
30Ni0.8Fe0.2O/70 Al2O3, and 30Ni0.7Fe0.3O/70Al2O3 samples. In
particular, the sizes were increased 2.23 fold compared to those in
the 30Ni/70Al2O3 sample before H2-reduction.
Fig. 4 shows the TEM image and TEM-elemental mapping on the
reduced 30Ni0.8Fe0.2O/70Al2O3 as a representative sample. The
scale bars of the images are 100 nm. Rectangular-shaped Ni, NiFe
alloy, and NiAl2O4 particles, approximately 30, 50, and 100 nm in
size, respectively, were observed in the reduced 30Ni0.8Fe0.2O/
70Al2O3 sample, and there was no significant aggregation between
the metal oxides. The particle sizes decreased with increasing
amount of Fe added, and there was little aggregation between the

Fig. 3. XRD patterns of 30NiO/70Al2O3 and 30Ni0xFeyO/70Al2O3 before and after pre-reduction.
328 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336

Fig. 4. TEM and elements-mapping images of 30Ni0.8Fe0.2O/70Al2O3 after pre-reduction.

metal oxides. This suggests that the Fe components existed
between the Ni particles, preventing any strong agglomeration
between them. The elemental mapping showed that all of the
components, Ni, Fe, Al, and O, were evenly distributed and their
concentrations were reliable as expected.
Fig. 5 displays the survey spectra derived from the quantitative
XPS analysis of the Ni2p, Fe2p, Al2p, and O1s peaks for all of the
reduced samples, viz. 30NiO/70Al2O3, 30Ni0.9Fe0.1O/70Al2O3,
30Ni0.8Fe0.2O/70Al2O3, and 30Ni0.7Fe0.3O/70Al2O3. The difference
between the 2p3/2 and 2p1/2 peaks was 17.49 eV in each case.
The 2p3/2 spin-orbital photoelectron of Ni before PSR was located
at a binding energy of 853.8–860.0 eV, which was assigned to
NiO in NiAl2O4 for all of the samples [29]. On the other hand,
the curves were slightly changed to a lower binding energy in the
three samples, 30Ni0.9Fe0.1O/70Al2O3, 30Ni0.8Fe0.2O/70Al2O3, and
30Ni0.7Fe0.3O/70Al2O3, corresponding to lower oxidation states of

Fig. 5. Survey spectra from quantitative XPS of the Ni2p, Fe2p, Al2p, and O1s peaks for the 30NiO/70Al2O3 and 30Ni0xFeyO/70Al2O3 catalysts after pre-reduction.
 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336
the Ni components, even though the area of the peaks was smaller.
From this result, it was deduced that the reduction potentials of Ni2
+
! Ni0 and Fe2+ ! Fe0 were 0.25 and 0.44 eV, respectively, and,
thus, that the reduction of Ni is performed more rapidly than that
of Fe in the 30NixFeyO/70Al2O3 samples, so the added Fe
ingredients should facilitate the reduction of Ni oxide. With
increasing concentration of Fe added, the peak intensities
according to Fe oxide increased. During PSR, Fe oxides can strongly
attract propane molecules, and Ni oxides can act as an oxygen
donor to the thermally cracked CH2CH4 or CH4 molecules from
propane in the formation of CH3CHO and CO as intermediates. In
contrast, the spin-orbital spectra of Fe2p3/2 and Fe2p1/2 for FeO in
FeAl2O4 over the 30NixFeyO/70Al2O3 samples revealed broad peaks
at 712.0 and 725.6 eV, respectively [30], and the difference
between the two orbitals, HOMO and LUMO, was 13.6 eV. The
peak locations were not changed, but the intensities were more
sharply dependent on the amount of Fe added. The Al2p and O1s
spin-orbital photoelectrons were located at binding energies of
76.4 and 533.0 eV, respectively, which were assigned to Al and O in
Al2O3 or NiAl2O4 for all of the samples. The curves were shifted to a
very slightly lower binding energy in the 30NixFeyO/70Al2O3
samples compared to 30NiO/70Al2O3. Additionally, the atomic
compositions for the O, Al, Ni, and Fe components obtained by XPS
analysis (%) after reduction are also compared in the right-hand
table. The atomic ratios for Ni/Fe were 3.26, 2.63, and 1.59 in
30Ni0.9Fe0.1O/70Al2O3, 30Ni0.8Fe0.2O/70Al2O3, and 30Ni0.7Fe0.3O/
70Al2O3, respectively, which differ from the initial amounts used in
the synthesis step. The amounts of Ni and Fe present on the surface
were not affected greatly by the amount inserted during synthesis,
which also indicates their high dispersion. In addition, the accurate
quantitative analysis of a surface by XPS analysis alone is difficult.
However, the atomic amount of Fe increased proportionally in the
order of 30Ni0.9Fe0.1O/70Al2O3, 30Ni0.8Fe0.2O/70Al2O3, and
30Ni0.7Fe0.3O/70Al2O3, thus these values seem to be somewhat
consistent.
Fig. 6. N2-adsorption/desorption isotherm curves (A) and pore size distributions determined from the BJH (Barrett–Joyner–Halenda) plots (B) of the 30NiO/70Al2O3 and
30Ni0xFeyO/70Al2O3 catalysts after pre-reduction.
329
Fig. 6 shows the adsorption–desorption isotherm curves of N2
at 77 K for the reduced samples, 30NiO/70Al2O3, 30Ni0.9Fe0.1O/
70Al2O3, 30Ni0.8Fe0.2O/70Al2O3, and 30Ni0.7Fe0.3O/70Al2O3. Using
Kelvin’s equation [31], the radius of the pores, in which capillary
condensation occurs actively, can be determined as a function of
the relative pressure (P/P0). The mean pore diameter, Dp, was
calculated from Dp = 4VT/S, where VT is the total volume of the
pores and S is the BET surface area. According to the IUPAC
classification, all of the isotherms belonged to type IV [32]. The
hysteresis slopes were observed at higher relative pressures in all
of the samples, indicating the presence of bulk mesopores formed
between the particles. The BET specific surface areas were
significantly higher in the 30NixFeyO/70Al2O3 samples (94.5–
100.9 m2 g1) than in the 30NiO/70Al2O3 one (56.67 m2 g1). In
general, the specific surface areas in regular particles are strongly
related to the particle sizes: the lower the particle size, the higher
the surface area. These results suggest that the particle sizes were
smaller in the 30NixFeyO/70Al2O3 samples due to the addition of
Fe. The total pore volumes increased with increasing amount of Fe
added, showing the same trend in all of the samples. The pore size
distribution (PDS) is an important characteristic for porous
materials. Among these methods, the BJH (Barrett–Joyner–
Halenda) plot provides a suitable method for the measurement
of micro- or meso-pores [33]. Through the BJH plot, the pore size
distributions and average pore diameters in the 30NixFeyO/
70Al2O3 samples were found to be slightly sharper and smaller,
depending on the amount of Fe added, than those in 30NiO/
70Al2O3.
Gas adsorption abilities on the 30NixFeyO/70Al2O3 catalysts
The reactivity of the catalyst is strongly associated with its
adsorption capacity for the reactant or intermediate gases. In
general, a catalyst having a strong adsorption capacity for these
gases exhibits superior catalytic activity. Chemisorption is a kind of
330 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336

adsorption which involves a chemical reaction between the surface

and the adsorbent: new chemical bonds are generated at the
adsorbent surface. An important aspect of chemisorption is in
heterogeneous catalysis, which involves molecules reacting with
each other via the formation of chemisorbed intermediates [34].
After the chemisorbed species combine, the product desorbs from
the surface. This study attempted the thermal programmed
chemisorption for propane gas and steam as the reactant feeds
and CO which is generated in the final stage. In the first step, tests
of C3H8-chemisorption were performed and the desorption curves
for chemisorbed C3H8 are exhibited in Fig. 7A. Additionally, the
evolution of the mass spectrometer signals (m/z) recorded during
propane desorption with O2 valence carriers over 30NixFeyO/
70Al2O3 is shown in Fig. 7B. Propane chemisorption experiments
were conducted in order to investigate the interaction of the
molecular species with the surface oxygen in the catalytic surfaces
derived from the 30NixFey/70Al2O3 samples. The C3H8 desorption
profiles were characterized over one broad temperature range, Fig. 8. CO-TPD profiles of the pre-reduced 30NiO/70Al2O3 and 30Ni0xFeyO/70Al2O3
400–600
C, corresponding to C3H8 desorption on the metal catalysts.
species. The temperature locations were almost the same for all
of the samples, but the areas of the curves were significantly larger similar to the intermediates and products produced during the
in the case of 30NixFeyO/70Al2O3. In particular, the desorbed area reforming reaction for propane.
was the largest in the case of 30Ni0.8Fe0.2O/70Al2O3, where it was CO-TPD experiments were performed for all of the samples, as
2.8 times larger than that for 30Ni/70Al2O3, which means that shown in Fig. 8. The majority of the adsorbed CO desorbs as CO2 at
considerably more C3H8 molecules were adsorbed on the surface of high temperatures, but some molecular desorption of CO occurs at
the bimetallic NiFeO surfaces than on the Ni surface. Otherwise, temperatures as low as 50–250
C and, indeed, CO desorption
the desorption curves were separated into three curves, and on the begins immediately upon the initiation of the temperature ramp
basis of mass spectroscopy, assigned to H2, CH4, CH3CHO, CO, and [36]. In this study, the CO desorption profiles were characterized
CO2 desorptions [35]. Fig. 7B presents the mass spectra for the over two broad temperature ranges in 30NiO/70Al2O3 centered at
desorbed molecules in O2 valence for the three desorption 350 and 600
C, corresponding to CO and CO2 desorption on the
temperatures, 500, 750, and 850
C. Signals at m/z = 2 (H2), 16 metal species, respectively. The temperatures decreased and the
(CH4), 28 (CO), 43 (CH3CHO), and 44 (CO2) were exhibited over the curve intensities increased significantly in the 30NixFeyO/70Al2O3
30Ni0.8Fe0.2O/70Al2O3 sample. The mass spectroscopy signals did samples, which mean that considerably more CO molecules were
not vary with the desorption temperature in any of the segmental adsorbed on the surface of the metallic NiFe than on the mono Ni
compounds, except for CO2. These segmental compounds are component. Additionally the adsorbed area was the largest in the

Fig. 7. C3H8-TPD profiles (A) and mass spectra (B) on the pre-reduced 30NiO/70Al2O3 and 30Ni0xFeyO/70Al2O3 catalysts.
 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336 331

Fig. 9. Correlation graphs of ln(C/Tm2) versus Tm deduced by Kissinger equation for the pre-reduced 30NiO/70Al2O3 and 30Ni0.8Fe0.2O/70Al2O3 catalysts.

30Ni0.8Fe0.2O/70Al2O3 sample. In general, a rapid catalytic reaction
occurs when many reactants are well-adsorbed over the catalyst.
On the other hand, water (H2O) molecules constitute the main
gas in hydrocarbon steam reforming. Water molecules are involved
in the water gas shift reaction to convert CO to CO2. The H2O-
desorption experiments for two representative samples, 30NiO/
70Al2O3 and 30Ni0.8Fe0.2/70Al2O3, were performed using a TG
instrument, and their activation energies were calculated from the
slopes, which were obtained from the plots [37] of ln(C/Tm2)
versus 1/Tm, as shown in Fig. 9. The activation energy was larger in
30Ni0.8Fe0.2O/70Al2O3 than in 30NiO/70Al2O3: the difference in the
activation energies reached 2.78 fold. Additionally, the water
desorption rate was higher in the 30Ni0.8Fe0.2O/70Al2O3 sample.
This means that the water molecules were absorbed better on the
surface of the catalyst having the larger desorption activation
energy. It is expected that the steam added to the propane feed gas
will adsorb on the surface of the Fe component rather than that of
Ni during the propane steam reforming reaction.
PSR performances over the 30NixFeyO/70Al2O3 catalysts
Fig. 10 shows the propane conversion and hydrogen selectivity
during propane steam reforming on the two representative
samples of 30NiO/70Al2O3 and 30Ni0.8Fe0.2O/70Al2O3, according
to the reaction temperature in the range from 500 to 800
C with an
interval of 50
C for 1 h at a GHSV 6000 h1. Depending on the
reaction temperature, both the propane conversion and hydrogen
selectivity increased in the two samples, and the propane
conversion was 100% above 650
C in both samples. However,
the rate of increase of the hydrogen selectivity was greater in the
30Ni0.8Fe0.2O/70Al2O3 catalyst than that in 30NiO/70Al2O3 and the
increase was particularly marked at 700
C in both samples. At
700
C, the hydrogen selectivity amounted to 86% in the
30Ni0.8Fe0.2O/70Al2O3 catalyst, whereas it was only 79% in
30NiO/70Al2O3 at the same temperature. Thus, on the basis of
this result, the optimum temperature was fixed at 700
C in this
study.
Fig. 11 exhibits the product distributions and the absolute
values for all of the samples evolved during propane steam
reforming for 1 h at 700
C for a GHSV of 6000 h1. Here, the
propane conversions were close to 100% in all of the samples,
however the absolute amounts of hydrogen generated differed
depending on the catalyst (Fig. 11A); the absolute value exceeded
80 mL in the 30Ni0.8Fe0.2O/70Al2O3 catalyst, which is more than the
value of 20 mL emitted in the 30NiO/70Al2O3 one. Regarding the
product distributions during PSR, there are only three molecules in
the 30NiO/70Al2O3 catalyst, viz. H2, CH4, and CO, as the main
products, whereas more CO2 gas was emitted in the case of the
30NixFeyO/70Al2O3 catalysts. This is evidence that the water gas
shift reaction proceeds readily during propane steam reforming
over the 30NixFeyO/70Al2O3 catalysts. However, no intermediates,
except for acetaldehyde and ethylene molecules, were observed in

Fig. 10. The propane conversion and hydrogen selectivity on 30NiO/70Al2O3 and 30Ni0.8Fe0.2O/70Al2O3 catalysts according to the reaction temperatures.
332 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336
Fig. 11. Product distributions (A) for all of the catalysts, and gas chromatography (B) and mass spectroscopy (C) results for the 30Ni0.8Fe0.2O/70Al2O3 catalyst during PSR.
the GC signal during PSR at 700
C, possibly because the reaction
temperature was too high. Thus, the reaction temperature was
reduced to 450
C in an attempt to identify any intermediates. As a
result, a small amount of ethylene (C2H4) molecules was seen in
the GC signal during PSR at 450
C, as shown in Fig. 11B. In order to
observe all of the intermediates evolved during PSR, mass
spectroscopy was used and the resultant signals are shown in
Fig. 11C: the signals at m/z = 14, 26, 28, and 29 were assigned to
CH2, C2H2, C2H4, and CH3CHO, respectively. The mechanism of CH4
steam reforming has been extensively studied [38], however, less
research has focused on the propane and higher hydrocarbon
steam reforming mechanisms [39]. In the present work, the solid–
gas mechanism involves the reactions between hydrocarbons
(C3H8, CH4, and C2H4) and/or an intermediate surface hydrocarbon
species with lattice oxygen at the NiFeO surface. Based on this
result, the mechanism in PSR was expected to be as follows: The
main reaction is accompanied by cracking to produce methane and
ethylene on the surface of metallic Ni in the catalysts (*) with the
possible hydrogenation of the latter. The cracking reaction is
C3H8 + * ! C2H4 + CH4. Here, C2H6 produced by the hydrogenation
of C2H4 was not detected in this study. The production of CH4 as an
intermediate was favored under our conditions and various
reactions proceeded on the surface of the catalysts: the
C2H4formed was converted to CH3CHO on the surface of the
oxidized metal in the catalyst and then converted to CH4 and CO.
After that, the CH4 was converted to H2 and CO. Finally, the steam
(H2O) enables the reduced metal species in the catalysts to recover
by delivering oxygen with the production of H2 (water gas shift
reaction).
C2H4 + *Ox ! CH3CHO + *Ox1,
CH3CHO + * ! CH4 + CO*,
CH4 + *Ox ! 2H2 + C*Ox,
C*Ox ! CO + *Ox1,
CO* ! CO + *,
CO + *Ox ! CO2 + *Ox1, (9)
H2O + *Ox1 ! H2 + *Ox (10)
Fig. 12 exhibits the C3H8 conversion and hydrogen selectivity
during propane steam reforming for all of the catalysts, 30NiO/
70Al2O3, 30Ni0.9Fe0.1O/70Al2O3, 30Ni0.8Fe0.2O/70Al2O3, and
30Ni0.7Fe0.3O/70Al2O3, at a time on stream of 10 h at 700
C for a
GHSV of 6000 h1. The propane was perfectly converted to the
products with 100% conversion and these perfect conversions were
maintained for 10 h in all of the samples. The hydrogen production
was the highest over the 30Ni0.8Fe0.2O/70Al2O3 sample, reaching
89% after 10 h, whereas it was 67% in the case of 30NiO/70Al2O3.
Generally, the presence of CO degrades the active catalyst, due to
catalyst poisoning by CO molecules [40]. The CO evolution was the
smallest in the 30Ni0.8Fe0.2O/70Al2O3 sample. On the other hand,
the hydrogen selectivity decreased significantly in the
30Ni0.7Fe0.3O/70Al2O3 sample. This is possibly because the
increase in the amount of Fe led to the acceleration of the
Fisher–Tropsch reaction (CO + H2 ! CH4), leading to the reverse
methane reforming reaction. Therefore, there is an optimal
amount of Fe of 0.2 mol. Based on the product distribution, the
introduction of an appropriate amount of Fe into the 30Ni/70Al2O3
catalyst during PSR has a favorable effect on the catalytic
performance, due to the enhancement of the water gas shift
reaction, resulting in less catalytic deactivation. Therefore, these
results highlight the synergic effect of Fe and Ni on the catalytic
performance in PSR.
Characteristics of the catalysts after PSR
(4)
The XRD patterns of the used 30NixFeyO/70Al2O3 catalysts were
(5) analyzed, in order to determine the structural changes in the metal
species of the catalysts after PSR, as shown in Fig. 13. The
(6) diffraction lines for all of the used catalysts were similar to those of
the fresh ones (the pre-reduced catalysts). Metallic Ni species after
(7) PSR were seen in all of the catalysts, and the intensities were the
strongest in the 30NiO/70Al2O3 sample, however the peaks were
(8) smaller and the (111) planes were shifted to lower angles in the
 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336
Fig. 12. Propane conversions and hydrogen productions versus reaction times for the 30NiO/70Al2O3 and 30Ni0xFeyO/70Al2O3 catalysts.
30NixFeyO/70Al2O3 samples. Using Scherrer’s equation, the crys-
tallite sizes estimated based on the (111) plane of the Ni formed in
the 30NiO/70Al2O3, 30Ni0.9Fe0.1O/70Al2O3, 30Ni0.8Fe0.2O/70Al2O3,
and 30Ni0.7Fe0.3O/70Al2O3 samples were 33.70, 27.86, 26.14, and
26.21 nm, respectively, which provide proof that the Ni particles
after the reaction were strongly aggregated in the 30NiO/70Al2O3
sample. On the other hand, the peaks which were assigned to
NiAl2O4 became somewhat bigger in the case of 30NixFeyO/
70Al2O3, which means that the NiO components remained in the
30NixFeyO/70Al2O3 samples.
Fig. 14 shows the survey spectra derived from the quantitative
XPS spectra of the Ni2p, Fe2p, Al2p, and O1s peaks for the used
catalyst after PSR. The peak locations for the 2p3/2 spin-orbital
photoelectron, which was assigned to Ni2+ in all of the catalysts,
Fig. 13. XRD patterns of the used 30NiO/70Al2O3 and 30Ni0xFeyO/70Al2O3 catalysts
after PSR.
333
did not change compared to those in the fresh catalysts, but the
intensities were greatly decreased in the 30NiO/70Al2O3 sample.
This trend was also observed for the Fe2p3/2 spin-orbitals, and the
peak decreased significantly when there were no Fe ions in the
catalysts. In particular, the peak intensity remains the strongest in
the 30Ni0.8Fe0.2O/70Al2O3 sample. Eventually, the reduced Ni was
re-oxidized by the Fe oxide during PSR, resulting in the formation
of CH3CHO and CO as intermediates. The observation of peak
separation in the Al2p spectra in the 30NiO/70Al2O3 sample is quite
unusual: the amount of aluminum oxide with reduced states at
around 75.0 eV was lower, but a new peak was observed at 78 eV
with a more highly oxidized state. This is considered to be due to
the conversion of the isolated aluminum from the Ni components
to Al(OH)3 during PSR [41]. This trend is the same in the O1s
spectra. It likely corresponds to more highly oxidized oxygen;
probably the O of the OH in Al(OH)3.
To determine the amounts and shapes of the carbon deposited
on each catalyst, the amounts of carbon deposited were measured
from the C1s-XPS analysis, as shown in Fig. 15. There is a peak at
286 eV which is assigned to carbon deposited on the surface of the
catalysts after PSR. It can be assumed to correspond to three main
kinds of carbon species, viz. C–O, C–C or C–H, as well as a small
amount of CNTs [42,43]. The peak locations were almost the same,
except for the 30Ni0.8Fe0.2O/70Al2O3 sample, where they were
shifted to a higher binding energy, corresponding to a carbon
component in a more highly oxidized state. It is estimated that the
carbon deposited on the catalysts was in the form of lumps of
carbon, and a very small amount of CNTs was produced. The peak
area, which corresponds to the amount of carbon deposited, was
the largest in the used 30NiO/70Al2O3 sample and the smallest in
the 30Ni0.8Fe0.2O/70Al2O3 sample, indicating that the level of
catalytic degradation caused by coke formation was reduced over
the latter. This shows that the carbon did not grow over the Fe sites,
suggesting that water could adsorb easily over them, indicating
334 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336

Fig. 14. Survey spectra from quantitative XPS of the Ni2p, Fe2p, Al2p, and O1s peaks for the 30NiO/70Al2O3 and 30Ni0xFeyO/70Al2O3 catalysts after PSR.

that Fe plays a role in changing CO to CO2, promoting the
production of hydrogen with less catalytic deterioration.
On the basis of the PSR performances and the physicochemical
analysis on the catalysts, in particular the mass spectroscopy
results, Scheme 1 presents the proposed PSR mechanism over
the30NixFeyO/70Al2O3 catalysts. During propane reforming, the
metallic Ni component plays an important role in the dehydro-
genation and thermal cracking resulting from the propane gases.
These gases are transformed into C2H4 and CH4 as intermediates
and acetaldehyde (CH3CHO) is generated by ethylene oxidation
over NiFeO. Then, acetaldehyde is thermally cracked catalytically
to produce CH4 and CO. The CH4 and CO obtained participate in
other reactions, such as the CH4-stem reforming reaction and the
CO–water gas shift reaction over Ni and FeO, respectively. Their
gas adsorption abilities were compared through H2O-TPD experi-
ments (Fig. 9). On the basis of the CO- and H2O-TPD experiments,
it can be inferred that water molecules are well adsorbed on the
Fe components and, thus, the CO-water gas shift reaction takes
place more predominantly over 30NixFeyO/70Al2O3 than over
30NiO/70Al2O3. Finally, the CO molecules obtained by CH4-SR
should be converted to CO2 and H2 via a secondary CO-WGS
reaction. On the other hand, the amount of CO2 molecules evolved
over the 30NiO/70Al2O3 sample was too small and, consequently,
CO molecules are deposited as carbon lumps on the 30NiO/
70Al2O3 catalyst surface, resulting in catalytic deactivation.
Contrary to our expectations, however, no deterioration of the

Fig. 15. Survey spectra from quantitative XPS of the C1s peaks for the 30NiO/70Al2O3 and 30Ni0xFeyO/70Al2O3 catalysts after PSR.
 K.M. Kim et al. / Journal of Industrial and Engineering Chemistry 46 (2017) 324–336
Scheme 1. The expected model for propane steam reforming over the 30Ni0xFeyO/70Al2O3 catalyst.
catalyst occurred. In this experiment, the addition of Fe oxide
contributed significantly to preventing sintering between the
inter-Ni particles. Therefore, Fe oxide as a promoter helps produce
a high hydrogen yield in the PSR reaction while inducing the
emission of CO2.
Conclusions
The goal of this study was to improve the catalytic stability of
the 30NiO/70Al2O3 catalyst through the introduction of Fe as a sub-
catalytic species. Three types of 30NixFeyO/70Al2O3 catalysts were
prepared and there existed an optimum Ni/Fe ratio, which was
Ni0.8:Fe0.2. The hydrogen yield in PSR was the highest on the
30Ni0.8Fe0.2O/70Al2O3 catalyst, reaching 83% with 100% propane
conversion. In addition, more C3H8 and CO gases adsorbed over the
30Ni0.8Fe0.2O/70Al2O3 catalyst, resulting in the formation of a
greater amount of CO2 gas. During PSR, C2H4, CH4, and CH3CHO
molecules were identified as intermediates. A trace amount of
carbon lumps was deposited over the 30Ni0.8Fe0.2/70Al2O3 catalyst
after the PSR reaction. Overall, this study proved that the
introduction of Fe along with Ni in PSR has a favorable effect on
the stable production of hydrogen gas, with significantly less
catalytic deactivation due to catalytic poisoning by CO molecules,
since these are transformed to CO2 through the water gas shift
reaction.
Acknowledgments
This work was supported by the Human Resource Training
Program for Regional Innovation and Creativity through the
Ministry of Education and National Research Foundation of Korea
(NRF-2015H1C1A1035639), and by the Basic Research Science and
Technology Projects through the National Research Foundation of
Korea Grant funded by the Ministry of Science, ICT & Future
335
Planning (No. 2015R1A1A3A04001268), for which the authors are
very grateful.
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