i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8

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Effect of metal addition to Ni/CeO2 catalyst on the

steam reforming reaction of methane

Yuji Tsuda a,*, Takenori Hirano b, Mitsuaki Echigo a,1

a
Energy Technology Laboratories, Osaka Gas Co., Ltd., 6-19-9, Torishima, Konohana-ku, Osaka 554-0051, Japan
b
Catalyst Research Inc., 1474, Okubo, Takaono-cho, Izumi-shi, Kagoshima 899-0401, Japan

highlights graphical abstract

Metal addition effect to Ni/CeO2 on

steam reforming reaction of CH4
was investigated.

The addition of V to Ni/CeO2 cata-
lyst increased the catalytic
activity.

Reducibility of Ni was enhanced by
the V addition.

NieV/GDC showed near-
equilibrium CH4 conversions even
at low temperatures.

article info abstract

Article history: In this study, the effect of metal addition (V, Co, Cu, Mo, or W) to Ni/CeO2 catalyst on the
Received 29 May 2023 steam reforming reaction of methane was investigated. The addition of Cu, Mo, or W
Received in revised form resulted in decreased catalytic activity. The catalytic activity of the Co added catalyst was
5 September 2023 not largely affected compared with that of the Ni/CeO2 catalyst. Meanwhile, the addition of
Accepted 26 September 2023 V increased the catalytic activity in the steam reforming reaction of methane. Therefore,
Available online 18 October 2023 the V added catalyst was analyzed in detail. NieV mixed oxide formation was confirmed in
the prepared state. After reduction, it was presumed that the NieV mixed oxide was
Keywords: transformed into Ni and the oxide of V. The V oxide was present near the metal-state Ni.
Supported Ni catalyst The Ni metal phase derived from the NieV mixed oxide may contribute to the positive
CeO2 effect of V addition to the Ni/CeO2 catalyst on the steam reforming reaction. Moreover,
Gadolinium-doped ceria (GDC) changing the support to gadolinium-doped ceria (GDC) confirmed the positive effect of V
Vanadium addition

* Corresponding author.
E-mail address: yu-tsuda@osakagas.co.jp (Y. Tsuda).
1
Present address: Department of Mechanical Engineering, Faculty of Science and Engineering, Tokushima Bunri University, 1314-1,
Shido, Sanuki, Kagawa 769-2193, Japan.
https://doi.org/10.1016/j.ijhydene.2023.09.272
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
938 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8
Methane steam reforming addition. In particular, the NieV/GDC catalyst enabled near-equilibrium CH4 conversions
Internal reforming even at low temperatures of 600e700  C.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
1. Introduction
In 2016, the Paris Agreement was adopted in the 21st Con-
ference of the Parties (COP21) as a global framework for
reducing CO2 emissions. Many countries have set a goal of
reducing their CO2 emissions to net zero by around 2050 [1,2].
To achieve net zero, many countries are undertaking various
approaches, including the implementation of electricity
derived from renewable energy sources such as solar, wind,
and geothermal power, and the development of technologies
for the efficient use of energy [3e5].
Fuel cell systems are one of the best candidates for power
generation with high efficiency, and are widely developed for
stationary and vehicle applications [6,7]. For stationary ap-
plications, the use of H2 rich reformed gas as a fuel obtained
from natural gas, which is mainly composed of methane, in
terms of infrastructure [8e10].
Regarding catalytic reforming methods, steam reforming
(SR), partial oxidation reforming (POX), auto thermal reform-
ing (ATR) and dry reforming (DR) have generally been studied
[11,12]. Among them, steam reforming method is the most
advantageous for increasing the efficiency of a fuel cell system
and has been commercialized [12]. Conversely, the arrange-
ment of the reforming reaction part in the fuel cell system can
be categorized into two types: external reforming and internal
reforming. In the former arrangement, the reforming reactor
operates separately from the fuel cell stack in the system, and
in the latter, the reforming part is arranged inside the fuel cell
stack. Both reforming arrangements can be adopted for a solid
oxide fuel cell (SOFC) system, which can be operated at high
temperatures such as 700e800  C. Internal reforming is
desirable for reducing the size and cost of an SOFC system
[13,14]. In an SOFC, the internal reforming reaction proceeds
in the anode electrode layer containing Ni. In particular, in the
case of an anode supported SOFC (ASC), the internal reforming
reaction proceeds in a sufficiently thick anode layer [13e16].
However, in the case of a metal supported SOFC (MSC), the
internal reforming reaction does not proceed sufficiently in a
very thin anode [17]. Moreover, for a MSC using doped ceria as
the oxygen-ion conducting ceramic, the operation tempera-
ture was noted to be 620  C or less [18]. In our previous study,
the power generation efficiency of a thin-film SOFC system
increased with the addition of an internal fuel reforming unit
at temperatures around 600e700  C [19]. Then, a high perfor-
mance internal reforming catalyst is desired for the thin-film
SOFC especially operated at 600e700  C.
Regarding the installation of an internal reforming catalyst
layer, into the MSC stack, it is preferable to have the thermal
expansion coefficient of the support similar to that of the cell
component. CeO2 base support can be more suitable than
Al2O3 base support for the internal reforming catalyst
concerning the thermal expansion coefficient. Noble metal
supported catalysts have high activity in the steam reforming
reaction of methane; however, they are costly [20e25]. Ni
supported catalysts are preferable compared with noble metal
supported catalysts because of their relatively higher activity
and lower cost. There are many reports on Ni/CeO2 for
methane steam reforming [26e29]. It has also been reported
that the catalytic activity of Ni/CeO2 improved by dissolving
the metal component (Zr, La, or Pr) in the CeO2 support
[30e33]. However, reports on the effect of metal addition in
the impregnation process of Ni to CeO2 support are scarce. On
the other hand, there are several reports about the additives,
such as B, Si, Mg, Cu or La, to Ni/Al2O3 for the steam reforming
reaction of methane [34e40].
Herein, the effect of metal addition (V, Co, Cu, Mo, or W), by
co-impregnation with Ni, to the Ni/CeO2 catalyst on the steam
reforming reaction of methane was studied for application to
internal reforming. As for the additive metals, V, Co, and Cu
were selected from the first transition series same as Ni.
Moreover, Mo from the second transition series and W from
the third transition series were selected. Those additives have
been rarely studied in Ni/CeO2 catalysts for methane steam
reforming.
Furthermore, in terms of the thermal expansion coeffi-
cient, gadolinium-doped ceria (GDC) a commonly used elec-
trode material in SOFCs, is suitable as the catalyst support in
the installation of the catalyst inside an SOFC stack for the
internal reforming reaction. Thus, the addition effect of V to
the Ni/GDC catalyst was also investigated.
2. Experimental
2.1. Catalyst preparation
Nickel catalysts supported on CeO2 (KCM Corporation, Japan)
and GDC (Ce0.8Gd0.2O1.9, KCM Corporation, Japan) were pre-
pared by the impregnation method. Ni(NO3)2$6H2O was used
as the nickel source. The metal component was added by co-
impregnation with Ni. VClO3, Co(NO3)2$6H2O, Cu(NO3)2-
$3H2O, (NH4)6Mo7O24$4H2O, and (NH4)6[H2W12O40] were used
as the sources of V, Co, Cu, Mo and W, respectively.
Ni(NO3)2$6H2O and the sources of additive metal components
were dissolved in pure water at room temperature. There-
after, oxide support powder was added to the solution. The
obtained mixture was evaporated in a steam bath at 80  C
and dried overnight in an oven at 60  C. The resulting powder
was calcined at 800  C for 4 h in air. In preparation, the input
values of Ni and additive component were 10 wt% and pri-
marily 3.3 wt%, respectively. The prepared powder was
pelletized and pulverized into 8e12 mesh.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8 939

2.2. Catalyst characterization

The chemical composition of the obtained catalysts was
analyzed through inductivity coupled plasma-atomic emis-
sion spectrometry (ICPeAES, Varian Inc.). The morphology of
the catalysts was analyzed through transmission electron
microscopy energy dispersive x-ray spectroscopy (TEMeEDX,
JEOL) analysis. The crystalline phase was identified through X-
ray diffraction (XRD, Rigaku) equipped with a Cu Ka radiation
source. The working conditions were 40 kV and 15 mA with a
scanning speed of 20 /min. The BET surface area was esti-
mated from nitrogen adsorption/desorption isotherms at 77 K.
The electronic state of Ni was evaluated by x-ray photoelec-
tron spectroscopy (XPS, JEOL) analysis.
2.3. Catalytic activity test
The catalytic activity test was performed in a 3/4 inch SUS316
tubular fixed-bed reactor vertically placed in a furnace under
atmospheric pressure. A catalyst, 5 ml in volume, was placed
at the center of the reactor, and the temperature was moni-
tored using a thermocouple, which was inserted at the bottom
of the catalyst layer. Before the activity test, the sample was
reduced at 600  C for 3 h in H2 at a flow rate of 500 ml/min as
pretreatment. The temperature dependence of the catalytic
activity was examined in the heating process with a supply of
28.6% CH4e71.4% H2O at a space velocity of 10,000 h1. Water
was added to the test gas by a syringe pump through a
vaporizer before the reactor. The sample was kept at each
temperature, for 30 min. The composition of the outlet gas
was analyzed through gas chromatography with a thermal
conductivity detector, and the flow rate was measured using a
wet flowmeter.
During the steam reforming reaction of methane, the
wateregas shift reaction proceeds simultaneously, as pre-
sented in Eqs. (1) and (2).
CH4 þ H2 O % CO þ 3H2
CO þ H2 O % CO2 þ H2
The CH4 conversion was defined as follows:
ðFCH4 in  FCH4 out Þ
CH4 conversion ð%Þ ¼  100
ðFCH4 in Þ
3. Results and discussion
3.1. Effect of metal addition to Ni/CeO2
The effects of adding V, Co, Cu, Mo, or W to the Ni/CeO2
catalyst on the steam reforming reaction of methane were
investigated. Table 1 shows the measured results of metal
loading and BET surface area of the prepared catalysts sup-
ported on CeO2. Table 1 also shows the BET value of bare CeO2
support used for each catalyst. Ni loading of each catalyst was
approximately 9 wt%.
Table 2(a) shows the CH4 conversion of the steam reform-
ing reaction of methane using each prepared catalyst at
600e800  C, GHSV ¼ 10,000 h1. Additionally, the equilibrium
values, calculated by the process simulation software Unisim
Design (Honeywell), are presented in Table 2(a). The balance of
carbon species calculated from the flow rates and gas com-
positions at the inlet and outlet of the reactor was almost the
identical in the catalytic activity tests. The addition of Cu, Mo
or W resulted in decreased CH4 conversion. The activity of the
Co added catalyst was not largely changed compared with
that of the Ni/CeO2 catalyst. However, the addition of V
increased CH4 conversion of Ni/CeO2 at 600e800  C to some
extent. Thus, it was confirmed that the V addition only
showed a positive effect on the increasing CH4 conversion
among the additives investigated in this study.
Table 2(b) and (c) show the CO2/CO ratio and the H2/CO
ratios of the outlet gas. As shown in Table 2(b) and (c), a
catalyst with a low CH4 conversion such as NieMo/CeO2
exhibited a high CO2/CO and H2/CO ratio, respectively.
For low CH4 conversion, a large amount of unreacted H2O
may have existed. Presumably, the equilibrium of the
wateregas shift reaction moved toward the CO2 and H2 for-
mation side. Conversely, the CO2/CO and the H2/CO ratios of
NieCo/CeO2 was relatively high compared with that of Ni/
CeO2, although their CH4 conversions were almost identical.
(1) Rezaei et al. reported that Co addition to FeeAl catalyst en-
hances the catalytic activity in the water-gas shift reaction
(2) [41]. In the case of Co addition to the Ni/CeO2 catalyst, it can be
presumed that the water-gas shift reaction was promoted
during the steam reforming reaction of methane. Khzouz et al.
(3)

where FCH4 in and FCH4 out represent the inlet and outlet gas Table 1 e Characteristics of obtained catalyst supported
flow rates of CH4, respectively. on CeO2 and CeO2 support.
The CO2/CO ratio was defined as follows: Catalyst Ni M BET
 loading loading surface
ðCCO2 out Þ (wt.%) (wt.%) area (m2/g)
CO2 CO ratio ¼ (4)
ðCCO out Þ
Ni/CeO2 9.5 - 0.79
where CCO out and CCO2 out represent the outlet gas concen- NieV/CeO2 9.2 2.4 0.69
trations of CO and CO2, respectively. NieCo/CeO2 9.2 3.2 0.99
The H2/CO ratio was defined as follows: NieCu/CeO2 9.4 3.7 0.45
NieMo/CeO2 9.2 5.2 1.03

ðCH2 out Þ NieW/CeO2 8.7 9.8 0.39
H2 CO ratio ¼ (5) CeO2 - - 9.71
ðCCO out Þ
M: V, Co, Cu, Mo or W.
where CH2 out represent the outlet gas concentration of H2.
940 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8

Table 2 e Catalytic activity of CH4 steam reforming Table 3 e Characteristics of each obtained V/CeO2, Ni/
reaction over supported on CeO2 catalysts. CeO2 and NieV/CeO2 catalysts.
(a): CH4 conversion (%) Catalyst Ni V BET
loading loading surface
Catalyst CH4 conversion (%)
(wt.%) (wt.%) area (m2/g)
600  C 650  C 700  C 750  C 800  C
V/CeO2 - 14.0 9.53
Equilibrium value 76.5 89.8 96.6 99.0 99.7 Ni/CeO2 9.5 - 0.79
Ni/CeO2 60.6 78.0 90.5 96.0 98.6 NieV/CeO2 9.2 2.4 0.69
NieV/CeO2 62.2 79.2 91.6 97.3 99.4 NieV/CeO2 (V  2) 9.3 4.8 0.52
NieCo/CeO2 59.7 77.4 90.3 96.1 98.1 NieV/CeO2 (V  4) 9.4 9.2 0.12
NieCu/CeO2 37.1 54.6 71.7 82.8 89.1
NieMo/CeO2 25.5 36.7 48.8 58.9 67.1
NieW/CeO2 32.0 51.9 75.5 91.6 97.5
of the V/CeO2 catalyst. Table 4 shows the methane conversion
(b): CO2/CO ratio using V/CeO2 in the steam reforming reaction of methane. As
Catalyst CO2/CO ratio shown in Tables 3 and 4, 14.0 wt% V/CeO2 was almost inactive
600  C 650  C 700  C 750  C 800  C in the steam reforming reaction of methane at 600e800  C.
NieV/CeO2 catalysts with different amounts of added V
Equilibrium value 1.45 0.86 0.60 0.48 0.40
Ni/CeO2 1.82 0.99 0.66 0.49 0.41
were prepared and evaluated. Table 3 also shows the char-
NieV/CeO2 1.76 1.01 0.66 0.50 0.57 acteristics of Ni/CeO2 without and with various amounts of
NieCo/CeO2 2.80 1.43 1.05 0.62 0.51 added V. The catalysts with two and four times the amount of
NieCu/CeO2 3.45 1.73 1.02 0.76 0.57 added V compared with NieV/CeO2 are denoted as NieV/CeO2
NieMo/CeO2 4.30 2.45 1.58 1.10 0.81 (V  2) and NieV/CeO2 (V  4), respectively. Table 4 also shows
NieW/CeO2 3.43 1.83 0.91 0.57 0.47
CH4 conversion in the steam reforming reaction of methane
(c): H2/CO ratio using NieV/CeO2 catalysts without and with various amounts
Catalyst H2/CO ratio of added V.
All V-added catalysts exhibited higher catalytic activity
600  C 650  C 700  C 750  C 800  C
than Ni/CeO2 at 600e800  C; thus, adding V in Ni/CeO2, has a
Equilibrium value 8.79 6.44 5.42 4.92 4.61
positive effect. The effect of V addition at high temperature
Ni/CeO2 10.40 7.01 5.66 5.00 4.66
around 800  C was not substantial, because the catalysts
NieV/CeO2 10.14 7.05 5.63 5.03 5.26
NieCo/CeO2 14.17 8.87 7.25 5.63 5.13 exhibited nearly equilibrium CH4 conversion. On the other
NieCu/CeO2 17.30 9.99 7.14 6.28 5.50 hand, at lower temperatures such as 600e700  C, CH4 con-
NieMo/CeO2 21.37 13.37 9.75 7.70 6.50 version increased with increasing amount of added V, which
NieW/CeO2 17.39 10.69 6.68 5.33 4.90 is inactive for steam reforming reaction of CH4 by itself. For
Reaction condition: 28.6% CH4 and 71.4% H2O (S/C ¼ 2.5). Catalyst example, as shown in Tables 3 and 4, CH4 conversion at 650  C
volume: 5.0 ml. S.V.: 10,000 h1. increased from 78.0% of Ni/CeO2 to 83.2% of NieV/CeO2 (V  4:
9.2 wt% V). Hence, the improvement of the Ni/CeO2 catalytic
activity by the addition of V may be attributed to the coexis-
reported that Cu addition to Ni/Al2O3 catalyst increase cata- tence of Ni and V.
lytic activity and coke formation resistance, indicating that Cu Fig. 1 shows the XRD patterns of Ni/CeO2, NieV/CeO2 and
particles increase the active particle size of Ni [36]. On the V/CeO2 in the as-prepared state. The peaks at 28.5 , 33.1 ,
other hand, the addition of Cu to Ni/CeO2 resulted in 47.5 ,56.4 and 59.3 correspond to CeO2 in all the spectra. The
decreased catalytic activity, in this test, as shown in Table 2. peaks at 37.6 and 43.4 correspond to NiO in the spectra of Ni/
This can be attributed to the differences in the support and CeO2 and NieV/CeO2. In the spectra of V/CeO2, the peaks
quantity of metal loading between the previous report and our correspond to CeO2 (;) and CeVO4 (▽). Although in the
study. spectrum of NieV/CeO2, low-intensity peaks were observed
As shown in Table 1, all the prepared catalysts exhibited
small BET surface areas. The BET surface areas of the prepared
catalysts decreased from that of bare CeO2 through the
Table 4 e CH4 conversion (%) of CH4 steam reforming
impregnation and calcination. The NieV/CeO2 catalyst, which
reaction over V/CeO2, Ni/CeO2 and NieV/CeO2 catalysts.
exhibited the highest catalytic activity, did not exhibit the
Catalyst CH4 conversion (%)
largest BET surface area among the prepared catalysts. Thus, a
clear correlation between catalytic activity and BET surface 600  C 650  C 700  C 750  C 800  C
area was not observed. Equilibrium value 76.5 89.8 96.6 99.0 99.7
V/CeO2 C0.1 C0.1 C0.1 1.7 0.7
3.2. Elucidation of the V addition effect Ni/CeO2 60.6 78.0 90.5 96.0 98.6
NieV/CeO2 62.2 79.2 91.6 97.3 99.4
NieV/CeO2 (V  2) 63.5 80.1 92.8 97.5 99.0
More in-depth evaluation of the effect of V addition to Ni/CeO2
NieV/CeO2 (V  4) 64.2 83.2 93.0 97.1 98.7
on its CH4 steam reforming activity was performed at
GHSV ¼ 10,000 h1. The catalytic activity of V/CeO2 was Reaction condition: 28.6% CH4 and 71.4% H2O (S/C ¼ 2.5). Catalyst
volume: 5.0 ml. S.V.: 10,000 h1.
investigated for reference. Table 3 presents the characteristics
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8
Fig. 1 e XRD patterns of Ni/CeO2, NieV/CeO2 and V/CeO2
catalysts.
around 35.5 and 44.5 (B). These peaks, which are different
from the CeVO4 peaks detected in the V/CeO2 spectrum,
correspond to another compound derived from Ni, V or both.
Fig. 2 shows the XRD patterns of the Ni/CeO2 catalyst
without and with various amounts of added V in the as-
prepared state. In the XRD patterns of the V-added catalysts,
Fig. 2 e XRD patterns of Ni/CeO2 and NieV/CeO2 catalysts
as-prepared state.
941
low-intensity peaks were observed at approximately 35.5 and
44.5 in addition to the peaks corresponding to NiO and CeO2.
As the amount of added V increased, these peaks intensi-
fied while the peaks corresponding to NiO weakened. These
low-intensity peaks presumably correspond to a NieV mixed
oxide. Furthermore, peaks corresponding to CeVO4 were also
observed in the spectra of NieV/CeO2 (V  2) and NieV/CeO2
(V  4). An increase in the amount of added V resulted in
increased amount of CeVO4 and NieV mixed oxide.
Fig. 3 shows the XRD patterns of each catalyst after cata-
lytic reaction. The peaks at 44.7 and 52.0 correspond to Ni
metal (-) in each catalyst. The peaks correspond to NiO and
the NieV mixed oxide observed for the as-prepared state
disappeared after the reduction and catalytic reactions.
In the XRD patterns of the NieV/CeO2 catalysts, the peaks
observed around 28.6 and 59.1 (,) may be assigned to VO2
(ICDS no.: 647,604), although the peaks of VO2 and CeO2
overlap. Presumably, the NieV mixed oxide in the prepared
state converted to Ni and VO2 after the reduction of the
catalyst.
Fig. 4 shows the TEM-EDX analysis results of NieV/CeO2
after catalytic reaction. Fig. 4(a) shows the entire TEM image of
the NieV/CeO2 catalyst. Fig. 4(b) shows an expanded view of
Area 1 corresponding to the CeO2 support and Fig. 4(c) shows
the EDX spectrum of Area 1. Further, Fig. 4(d) shows an
expanded view of Area 2, and Fig. 4(e) shows the corre-
sponding EDX spectrum. In Area 1, Ni and Ce were primarily
detected, whereas V was hardly detected. Meanwhile, in
Area 2, Ni and V were primarily detected but Ce exhibited low
presence. In Fig. 4(d), the light and dark areas correspond to Ni
and V, respectively. Thus, mainly Ni and V existed in Area 2.
These results, suggest that most amount of V was present in
the vicinity of Ni. Additionally, the results of the EDX mapping of
oxygen, shown in Fig. 4(f), indicated that V was in the oxide state.
Fig. 3 e XRD patterns of Ni/CeO2 and NieV/CeO2 catalysts
after catalytic reaction.
942 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8

Fig. 4 e TEM images and EDX spectrums of after catalytic reaction NieV/CeO2 catalyst. (a) Entire TEM image, (b) TEM image of
Area 1 (around CeO2 support), (c) EDX spectrum of Area 1, (d) TEM image of Area 2 (coexistence area of Ni and V) and (e) EDX
spectrum of Area 2 (f) EDX mapping of oxygen.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8
Fig. 5 e XPS spectra for Ni 2p 3/2 of before catalytic reaction catalysts (a) Ni/CeO2 and (b) NieV/CeO2.
The presence of the Ni metal derived from the NieV mixed oxide
can contribute to the positive effect of adding V to the Ni/CeO2
catalyst on the steam reforming reaction.
Fig. 5(a) and (b) show the XPS spectra for Ni 2p 3/2 of Ni/
CeO2 and NieV/CeO2 of before catalytic reaction, respectively.
In Fig. 5(a) and (b), a broad peak was detected around 854 eV in
both catalysts before reaction. Our peak separation results
indicate that both catalysts contain peaks correspond to Ni
and Ni(OH)2 or intermediate state before the catalytic reaction.
Peaks correspond to Ni(OH)2 or intermediate state were
detected around 854.8 eV in both catalysts. The binding energy
correspond to the Ni peak in Ni/CeO2 (852.8 eV) was lower than
that of the NieV/CeO2 (853.3 eV). The peak intensity of Ni
 
0
Peak area of Ni
Percentage of Ni in all Ni states ð%Þ ¼    100
0
0 2þ
Peak area of all Ni ðNi þ Ni
943
metal was slightly higher for the NieV/CeO2 than that of the
Ni/CeO2.
Fig. 6(a) and (b) show the XPS spectra for Ni 2p 3/2 of Ni/
CeO2 and NieV/CeO2 of after catalytic reaction, respectively.
As shown in Fig. 6(a) and (b), peaks correspond to Ni and
Ni(OH)2 or intermediate state were also detected in both cat-
alysts after the catalytic activity test. The peak intensity of Ni
metal was evidently higher for NieV/CeO2 than for the Ni/
CeO2 catalyst, implying that the Ni on NieV/CeO2 is more
metallic than on Ni/CeO2.
Table 5 summarizes the results of the XPS analysis after
catalytic reaction. The percentage of Ni0 in all Ni states was
determined as follows:
(6)
944 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8

Fig. 6 e XPS spectra for Ni 2p 3/2 of after catalytic reaction catalysts (a) Ni/CeO2 and (b) NieV/CeO2.

As shown in Table 5, the percentage of Ni0 in all the Ni shows the characteristics of the Ni/GDC and NieV/GDC cata-
states was higher in NieV/CeO2 than in Ni/CeO2. The increase lysts. Table 7 shows the CH4 conversion in the steam
in Ni0 percentage might contribute to the positive effect of reforming reaction of methane using Ni/GDC and NieV/GDC
adding V to Ni/CeO2 on the steam reforming reaction. at 600e800  C, GHSV ¼ 10,000 h1. As shown in Tables 4 and 7,
the catalytic activity of Ni/GDC was higher than that of Ni/
3.3. Effect of adding V to Ni/GDC CeO2 catalyst. The result corresponds to a previous report [29].
The report noted that the oxide ion conductivity of GDC may
The effect of adding V to the Ni/GDC catalyst on the steam benefit the catalytic activity in the steam reforming reaction of
reforming reaction of methane was investigated. Table 6 methane. As shown in Table 7, the catalytic activity of NieV/
GDC was higher than that of the Ni/GDC at 600e800  C.
Particularly, the catalytic activity of Ni/GDC at 600  C was
substantially enhanced from 64.7% to 71.2% by the addition of
Table 5 e Binding energies of the Ni 2P3/2 and percentage
of Ni0 in all Ni states analyzed by XPS measurement for
after catalytic reaction catalysts of Ni/CeO2 and NieV/
CeO2. Table 6 e Characteristics of obtained catalysts supported
Catalyst Ni 2p3/2 (eV) Percentage of on GDC.
Ni0 in all Catalyst Ni loading V loading BET surface area
Ni0 Ni2þ
Ni states (%) (wt.%) (wt.%) (m2/g)
Ni/CeO2 851.8 854.6 11 Ni/GDC 9.4 - 1.98
NieV/CeO2 851.8 854.8 30 NieV/GDC 9.6 3.1 1.74
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8 945

Table 7 e CH4 conversion (%) of CH4 steam reforming

reaction over catalysts supported on GDC.
Catalyst CH4 conversion (%)

600 C 650  C 700  C 750  C 800  C
Equilibrium value 76.5 89.8 96.6 99.0 99.7
Ni/GDC 64.7 80.1 91.0 95.2 97.9
NieV/GDC 71.2 84.7 94.0 98.3 99.6

Reaction condition: 28.6% CH4 and 71.4% H2O (S/C ¼ 2.5). Catalyst
volume: 5.0 ml. S.V.: 10,000 h1.

V. Thus, the positive effect of V addition was also confirmed

for the Ni/GDC catalyst. Notably, the NieV/GDC catalyst
enabled near-equilibrium CH4 conversions even at low tem-
peratures of 600e700  C.
Fig. 7 shows the XRD patterns of the as-prepared Ni/GDC
and NieV/GDC catalysts. As shown in the figure, diffraction
peaks corresponding to NiO and GDC were mainly detected.
In the XRD patterns of the NieV/GDC and NieV/CeO2 cata-
lysts, low-intensity peaks were observed at approximately
35.5 and 44.5 , which correspond to the NieV mixed oxide.
Additionally, the peaks corresponding to CeVO4 were
observed clearly in the XRD patterns of the NieV/GDC cata-
lyst. Fig. 8 shows the XRD patterns of the Ni/GDC and NieV/
GDC catalysts after catalytic reaction. In the XRD pattern of
the NieV/GDC, the peaks observed at 28.6 and 59.1 may be
assigned to VO2, similar to the case of the Ni/CeO2 catalyst.
The positive effect of adding V to Ni/GDC on the steam
reforming reaction was also attributed to the presence of Ni
and VO2 derived from the NieV mixed oxide after
preparation.
Fig. 7 e XRD patterns of Ni/GDC and NieV/GDC catalysts as-
prepared state.
Fig. 8 e XRD patterns of Ni/GDC and NieV/GDC catalysts as
after catalytic reaction.
Fig. 9 shows the TEM-EDX analysis results of the NieV/GDC
catalyst after catalytic reaction. Fig. 9(a) shows the entire TEM
image of the NieV/GDC catalyst. Fig. 9(b) and (c) show an
expanded view of Area 1 corresponding to the GDC support
and the corresponding EDX spectrum, respectively. Fig. 9(d)
and (e) show an expanded view of Area 2 and the corre-
sponding EDX spectrum, respectively. In Area 1, Ni and Ce
were mainly detected, while V was hardly observed. Mean-
while, in Area 2, Ni and V were mainly detected while Ce
exhibited low presence. Thus, most amount of V is present in
the vicinity of Ni in the NieV/GDC catalyst similar to NieV/
CeO2.
From these results, the effect of adding V to Ni/CeO2 or Ni/
GDC can be considered as follows. In the as-prepared NieV/
CeO2 and NieV/GDC catalysts, Ni exists in two major states,
namely NiOesupport oxide (support ¼ CeO2 or GDC) and NieV
mixed oxide. Following reduction, these states are trans-
formed into Ni in the support oxide and in the vicinity of VO2,
respectively. The improved catalytic activity in the steam
reforming reaction of methane is attributed to the Ni metal
derived from the NieV mixed oxide.
To evaluate the performance of NieV/GDC as an inter-
nal reforming catalyst, catalytic activity test and durability
test for 100 h were conducted using a simulated reformed
gas: 11.4% CH4, 39.3% H2, 2.6% CO, 8.6% CO2 and 38.1% H2O.
The composition of the simulated reformed gas was set to
be the outlet gas of external reformer that about 50% of
methane had reformed. Table 8 shows the temperature
dependence of the catalytic activity in methane conversion
using the NieV/GDC catalyst and the simulated reformed
gas. Despite small variations compared with shown in
Table 7, methane conversion rates near the equilibrium
composition were obtained even under the simulated
reformed gas. Fig. 10 shows the result of the durability test
conducted for 100 h at 750  C. As shown in Fig. 10,
946 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8

Fig. 9 e TEM images and EDX spectrums of after catalytic reaction NieV/GDC catalyst. (a) Entire TEM image, (b) TEM image of
Area 1 (around GDC support), (c) EDX spectrum of Area 1, (d) TEM image of Area 2 (coexistence area of Ni and V) and (e) EDX
spectrum of Area 2.

methane conversion, CO concentration, and CO2 concen- After the durability test for 100 h, the amount of carbon
tration were stable during 100 h. NieV/GDC catalyst did not deposited on the catalyst surface was analyzed by combustion
degrade for 100 h under the operating conditions expected in an oxygen stream. The result was shown in Table 9. Addi-
for an internal reforming catalyst. tionally, Table 9 shows the carbon content of Ni/CeO2, NieV/
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 9 3 7 e9 4 8
Table 8 e CH4 conversion (%) of assumed reforming gas
over NieV/GDC.
Catalyst CH4 conversion (%)

600 C 650  C 700  C 750  C
Equilibrium value 47.6 75.4 91.4 97.4
NieV/GDC 48.2 71.3 88.1 94.9
Reaction condition: 11.4% CH4, 39.3% H2, 2.6% CO, 8.6% CO2 and
38.1% H2O (S/C ¼ 2.6). Catalyst volume: 5.0 ml. S.V.: 10,000 h1.
Fig. 10 e Durability test for 100 h under assumed reforming
gas over NieV/GDC catalyst. Reaction condition: 11.4% CH4,
39.3% H2, 2.6% CO, 8.6% CO2 and 38.1% H2O (S/C ¼ 2.6).
Temperature: 750  C. Catalyst volume: 5.0 ml. S.V.: 10,000
h¡1.
Table 9 e The amount of carbon deposition after reaction.
Catalyst Carbon
deposition
(mmol g1cat)
Ni/CeO2 after initial activity test
NieV/CeO2 after initial activity test
Ni/GDC after initial activity test
NieV/GDC after initial activity test
NieV/GDC after durability test for 100 h
CeO2, Ni/GDC, and NieV/GDC catalysts following the tests for
initial catalytic activity.
In the catalysts after initial activity tests, NieV/GDC
exhibited a similar amount of carbon content as the Ni/CeO2
and NieV/CeO2. The carbon amounts of 0.1 mmol g1cat or less
were detected as shown in Table 9. Moreover, no substantial
increase was observed in the carbon amount after from the
initial to the 100 h durability test. The amount of carbon
deposited on NieV/GDC after the 100 h durability test was
similar to or less than that on the methane steam reforming
catalysts reported in the literature wherein carbon deposition
has been noted to have little contribution to catalyst degra-
dation [26,31,40,42]. For example, it was reported that various
amounts of carbon from ~0 to 0.21 mmol g1cat were observed
on 2 kinds of Ni/CeO2 and 6 kinds of Ni/CeeZrO2 catalysts after
steam reforming reaction of CH4 for 10 h at 900  C, and the
carbon formations do not cause to the deactivations of the
947
catalysts [31]. The report also mentioned that the carbon
deposition of 1.31 mmol g1cat mainly related to the deacti-
vation of Ni/Al2O3 catalyst after the reaction [31].
Consequently, carbon deposition is considered to have
800  C little contribution to the activity of the NieV/GDC catalyst
99.2 during the 100 h durability test. On the other hand, in Ni
96.9 supported NiOeMgO catalyst, durability tests for up to 1000 h
have been conducted [43]. Such long-term durability tests will
be required to the NieV/GDC catalyst for the practical use.
4. Conclusion
The effects of metal addition (V, Co, Cu, Mo, or W) to the Ni/
CeO2 catalyst in the steam reforming reaction of methane
were investigated, and the following results were obtained.
Among the additive metals investigated in this study, the
addition of V shows positive effect for the catalytic activity of
Ni/CeO2 in the steam reforming reaction of methane. From the
result of XRD of the NieV/CeO2 catalyst in the prepared state,
it was confirmed that NieV mixed oxide and NiO were formed
in the catalyst. And, from the results of XRD and TEM-DEX of
the NieV/CeO2 catalyst after the initial activity test, it was
supposed that the NieV mixed oxide was transformed into Ni
and the oxide of V, which was present near the Ni metal. From
the results of XPS, the Ni on NieV/CeO2 is more metallic than
that on Ni/CeO2. Activation by the Ni metal derived from the
NieV mixed oxide contribute to the increase of methane
steam reforming activity of the Ni/CeO2 catalyst by the addi-
tion of V. Moreover, it was confirmed that the addition of V
improved the catalytic activity of Ni/GDC in the steam
reforming reaction of methane. The NieV/GDC catalyst
enabled near-equilibrium CH4 conversions even at low tem-
peratures of 600e700  C, GHSV ¼ 10,000 h1. In terms of the
thermal expansion coefficient, GDC a commonly used elec-
trode material in SOFCs. Thus, the NieV/GDC catalyst may be
better suited for internal reforming in SOFCs.
0.06
0.06
0.07 Declaration of competing interest
0.10
0.08
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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