Hindawi

International Journal of Energy Research

Volume 2023, Article ID 3950678, 18 pages
https://doi.org/10.1155/2023/3950678

Research Article
Effect of Sr Substitution on the Novel La1-xSrxCo0.5Ni0.5O3-δ
Perovskite-Type Catalysts for Hydrogen Production in Ethanol
Steam Reforming

Zicheng Shao,1 Shian Li ,1 Yuhang Jiang,1 Zhongwen Cai,1 Qiuwan Shen ,1

Guogang Yang,1 and Bengt Sunden2
1
Marine Engineering College, Dalian Maritime University, Dalian, China
2
Department of Energy Sciences, Lund University, Lund, Sweden

Correspondence should be addressed to Shian Li; lishian@dlmu.edu.cn and Qiuwan Shen; shenqiuwan@dlmu.edu.cn

Received 18 August 2022; Revised 22 September 2022; Accepted 29 September 2022; Published 4 February 2023

Academic Editor: Rafael M. Santos

Copyright © 2023 Zicheng Shao et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

La1-xSrxCo0.5Ni0.5O3-δ perovskites with different substitution of La by Sr have been firstly synthesized and applied as catalysts for
ethanol steam reforming (ESR). The effect of partial Sr substitution on the performance and stability of La1-xSrxCo0.5Ni0.5O3-δ for
ESR was investigated. The synthesized samples were characterized by XRD, SEM, BET, and EDS techniques. The results show that
with the increase of substitution of La by Sr, the pore size and surface area of La1-xSrxCo0.5Ni0.5O3-δ perovskite increase. The
doping of Sr causes changes in the specific surface area, pore volume, and pore size of the catalyst, which in turn causes
changes in its catalytic activity. Meanwhile, La0.1Sr0.9Co0.5Ni0.5O3-δ with a highest SBET presents the highest ethanol conversion
rate among all the samples. The modifications of catalyst characteristics caused by the Sr substitution in La1-xSrxCo0.5Ni0.5O3-δ
directly affect its catalytic performance in the ESR. What is more, the influences of operating parameters on the catalytic
activity of La0.1Sr0.9Co0.5Ni0.5O3-δ were studied in detail, and the optimum conditions were determined and applied for
stability experiments. When the temperature is lower than 500°C, the selectivity of gas products is most likely affected by the
dehydrogenation of ethanol and the decomposition of acetaldehyde. Meanwhile, the improving hydrogen selectivity and
reducing the formation of by-products can be achieved by increasing the reaction temperature. The best catalytic performance
for hydrogen production was achieved with La0.1Sr0.9Co0.5Ni0.5O3-δ which presented the highest ethanol conversion (98.7%)
under the optimal reaction conditions. La0.1Sr0.9Co0.5Ni0.5O3-δ perovskites with higher strontium degree of substitution
exhibited an excellent activity and stability of the catalysts derived.

1. Introduction as temperature, pressure, and steam ethanol ratio on the

With the rapid development of industry, hydrogen energy is
one of the attractive measures for solving the energy supply
security and the greenhouse gas emission. It can be stored
and transported conveniently and utilized in multiple ways.
Currently, as a kind of energy carrier with high calorific
value and high environmentally friendly, hydrogen has been
universally acknowledged as one of the potential fuels to
substitute for traditional fossil fuels [1, 2]. Pashchenko con-
cluded that thermochemical recuperation can be used as an
on-board hydrogen production technology and conducted
a series of studies on the effects of operating parameters such
heat recovery rate [3]. In addition, they also studied the fea-
sibility of using the heat contained in the outlet flue gas for
ethanol steam conversion [4].
In recent years, the ethanol steam reforming (ESR) tech-
nology is known as the hot spot in the field of research. Eth-
anol, as a new fuel, can reduce the greenhouse gas emissions
by 70% to 90% compared to fossil energy [5]. In the current
situation of increasingly scarce energy, the use of ethanol
new energy technology has important social and economic
significance [6]. Anil et al. reviewed the nickel-based cata-
lysts for hydrogen production from ethanol steam reforming
since 2000 and elucidated the importance of preparation
2 International Journal of Energy Research
Gas generator
Micro-injection
pump
Mass fow
controller
Gas analyzer
Data collection unit
Figure 1: Experimental setup for ESR.
methods and carrier modifiers to the morphology of the cat-
alysts and the reduction of carbon deposition [7]. In addi-
tion, the role of operating conditions such as water and
ethanol feed ratio and temperature with carbon generation
were interrelated, which is one of the focuses of this work [8].
Bioethanol fuel is widely concerned in the application of
resources because of its liquid nature, safety, small volume,
and other advantages [9]. At present, H2 production from
ethanol steam reforming is favored by the Proton Exchange
Membrane Fuel Cell (PEMFC) field because of its reasonable
economy and simple technology.
C2 H5 OH + 3H2 O ⇒ 2CO2 + 6H2 ð1Þ
The development of catalysts for H2 production by eth-
anol steam reforming mainly focuses on the unique struc-
ture of catalysts [10–12]. The catalysts applied to the
ethanol steam reforming can be divided into two categories:
noble metal catalysts represented by platinum and nonnoble
metal catalysts dominated by transition metals.
An et al. prepared a nickel-aluminum-based catalyst for
ethanol steam reforming to produce hydrogen by coprecipi-
tation [13]. They found that after the addition of Cu, due to
the synergistic effect of Ni-Cu, the conversion of ethanol in
different temperature ranges increased, and ethanol can be
completely converted at 500°C. Cortazar et al. showed that
10 wt% NiO/CaO bifunctional catalyst performs well in
adsorption enhanced ethanol steam reforming at 600-
750°C [14]. Martinelli et al. discussed the effect of sodium
loading on Pt/ZrO2 during ethanol steam reforming [15].
Grzybek et al. revealed the key importance of the precise
optimization of the K loading and dispersion on the Co|α-
Al2O3 catalyst for efficient hydrogen production via the eth-
anol steam reforming process [16]. The Ni/SiCxOy catalyst,
synthesized by Guo et al., showed that the ethanol conver-
sion and selectivity of H2 were still up to 91% and 72% after
Tube furnace
Float fowmeter
N2
Dryer-fler unit
210 min, respectively [17]. Niazi et al. compared the effects
of copper, magnesium, and cobalt on Ni-Ce supported cata-
lysts for ethanol steam reforming [18]. They found that the
nature of second metal has a strong influence on the catalyst
selectivity for H2 production. Among them, supported
nickel-based catalysts are the most widely developed and
applied, which have high H2 selectivity and catalytic activity
[19]. However, supported catalysts have some unavoidable
disadvantages, such as uneven distribution of active compo-
nents, easy poisoning, and short service life [20, 21].
Perovskite metal oxides have stable structures and flexi-
ble tunability of physicochemical properties, making them
one of the suitable choices for hydrogen production catalysts
[22]. For a typical ABO3 perovskite-type structure, the A-site
ion is generally an alkaline earth element ion with a larger
ion radius; the B-site ion is generally a transition metal ele-
ment ion with a smaller ion radius, and the transition metal
ion forms an octahedral coordination with six oxygen ions.
Perovskite-type catalysts have high mid-to-high temperature
activity and excellent thermal stability. Studies have shown
that if the A/B element of the perovskite-type metal oxide
is partially substituted, its crystal structure remains basically
unchanged, while some of its physical and chemical proper-
ties will be adjusted.
Alkaline earth metals such as La, Sr, and Ba are used as
the A-site metal, or transition metal elements such as Ni
and Co are used as B-site metals to adjust the physicochem-
ical properties of the perovskite catalyst, which is one of the
main ways to improve the stability and carbon resistance of
perovskite catalyst for H2 production by ethanol steam
reforming [23, 24]. Marinho et al. studied the performance
of nickel-based catalysts derived from LaNiO3 and LaNiO3
perovskite-type oxides supported by CeSiO2 in ESR [25].
The results showed that the initial ethanol conversion of
LaNiO3 reached 97%, while that of LaNiO3/CeSiO2 was only
85%. However, LaNiO3/CeSiO2 exhibits better stability
because the oxygen in cerium is transferred to metal
International Journal of Energy Research 3

1.0

0.8

CO yield (mol/mol ethanol)

0.6

0.4

0.2

0.0
0 100 200 300 400

Time (Min)
Sr 0.0 Sr 0.5
Sr 0.1 Sr 0.9
(a)
1.0

0.8
CO2 yield (mol/mol ethanol)

0.6

0.4

0.2

0.0

0 100 200 300 400

Time (Min)
Sr 0.0 Sr 0.5
Sr 0.1 Sr 0.9
(b)

Figure 2: Continued.
4 International Journal of Energy Research

0.4

CH4 yield (mol/mol ethanol)

0.3

0.2

0.1

0.0

0 100 200 300 400

Time (Min)
Sr 0.0 Sr 0.5
Sr 0.1 Sr 0.9
(c)
5.0

4.5

4.0
H2 yield (mol/mol ethanol)

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0
0 100 200 300 400

Time (Min)
Sr 0.0 Sr 0.5
Sr 0.1 Sr 0.9
(d)

Figure 2: Product yield over La1-xSrxCo0.5Ni0.5O3-δ for ethanol steam reforming: (a) CO yield; (b) CO2 yield; (c) CH4 yield; (d) H2 yield.

particles through the metal carrier interface and reacts with perovskite catalyst in ESR reaction. The experimental results
carbon, which inhibits the formation of carbon to a certain indicate that the Sr-doped catalyst exhibits excellent catalytic
extent. Therefore, if the lanthanide nickel-based perovskite activity and thermal stability compared to the other element-
catalyst can overcome the deactivation, it will have greater doped catalysts studied [27]. Esposito indicated that sup-
application potential. Wang et al. developed the ESR porting perovskite LaNiO3 on SBA-15 resulted in reduced
perovskite-type metal oxide catalyst, La1-xCaxFe1-xCoxO3 carbon deposition. The physical and chemical properties of
(x = 0:3, 0.5), which has high hydrogen selectivity and ther- synthetic compounds can be controlled by carefully chang-
mal stability [26]. Ma et al. studied the effect of A-site substi- ing the parameters affecting different synthetic steps, which
tution on the catalytic performance and stability of LaCoO3 is a unique feature of sol-gel method [28]. It is precisely
International Journal of Energy Research 5

1.0

0.8

Ethanol conversion (100%) 0.6 1.0

0.8

0.4 0.6

0.4

0.2
0.2
0.0

0.0
0 100 200 300 400

Time (Min)
Sr 0.0 Sr 0.5
Sr 0.1 Sr 0.9
(a)
80

70

60

50
Selectivity (%)

40

30

20

10

0
𝛿
𝛿

𝛿
3-
3-

3-

3-
5O
5O

5O

5O
.
.

.
i0
i0

i0

i0
5N
5N

5N

5N
0.
0.

0.

0.
O
Co

O
.1 C

.5 C

.9 C
La

r0

r0

r0
9S

5S

1S
0.

0.

0.
La

La

La

CO CH4
CO2 H2

(b)

Figure 3: (a) Comparison of ethanol conversion over La1-xSrxCo0.5Ni0.5O3-δ for ethanol steam reforming. (b) Product selectivity of La1-x
SrxCo0.5Ni0.5O3-δ catalysts at different Sr doping levels.

because of the characteristics of the sol-gel method that it is LaCoO3 perovskite catalyst has been used in ESR; how-
possible to accurately control the proportion of A/B doping ever, its catalytic activity and stability need to be further
elements in perovskite. improved. Therefore, appropriate substitution of the A- or
6 International Journal of Energy Research

1.4

1.2

1.0

CO yield (mol/mol ethanol) 0.8

0.6

0.4

0.2

0.0
0 100 200 300 400

Time (Min)
500°C 600°C
550°C 650°C
(a)
1.0

0.8
CO2 yield (mol/mol ethanol)

0.6

0.4

0.2

0.0
0 100 200 300 400

Time (Min)
500°C 600°C
550°C 650°C
(b)

Figure 4: Continued.
International Journal of Energy Research 7

0.4

CH4 yield (mol/mol ethanol)

0.2

0.0
0 100 200 300 400

Time (Min)
500°C 600°C
550°C 650°C
(c)
5

4
H2 yield (mol/mol ethanol)

0
0 100 200 300 400

Time (Min)
500°C 600°C
550°C 650°C
(d)

Figure 4: Product yield of La0.1Sr0.9Co0.5Ni0.5O3-δ for ethanol steam reforming at different reaction temperatures: (a) CO yield; (b) CO2
yield; (c) CH4 yield; (d) H2 yield.

B-sites is one of the effective ways to improve its catalytic lysts, namely, La1-xSrxCo0.5Ni0.5O3-δ (x = 0, 0.1, 0.5, 0.9, des-
performance [29]. Perovskite powder samples, with a homo- ignated as LSCN), in which the A-site is partially substituted
geneous distribution of components on the atomic scale by Sr, for hydrogen production by steam reforming of etha-
through a technology of low temperature synthesis and with nol. The influence of Sr substitution on the microscopic
full control of the finite product microstructure, were syn- characteristics of the catalyst on the catalytic performance
thesized by sol-gel method. The purpose of this work is to was studied by means such as XRD, SEM, BET, and EDS
study the performance of La-Co-Ni-based perovskite cata- characterization. In addition, the effects of reaction
8 International Journal of Energy Research
1.0
0.8
Ethanol conversion (100%)
0.6
1.0
0.8
0.4
0.6
0.4
0.2
0.2
0.0
0.0
0 100 200
Time (Min)
500°C
550°C
Figure 5: Ethanol conversion of La0.1Sr0.9Co0.5Ni0.5O3-δ for ethanol steam reforming at different reaction temperatures.
temperature, ratio of S/C, and steam flow rate on ESR per-
formance were investigated and optimized. Furthermore,
the stability test of the optimal catalyst for ESR process
was applied.
2. Material and Methods
2.1. Catalyst Synthesis. LSCN was synthesized by the sol-gel
method in this study. Analytical pure La (NO3)3·6H2O, Sr
(NO3)2, Ni (NO3)2, and Co (NO3)2·6H2O are used as metal
nitrate raw materials; citric acid and ethylenediaminetetra-
acetic acid (EDTA) are used as complexing agents. For the
specific preparation steps, refer to our previous research [30].
2.2. Catalyst Characterization. The surface morphology and
chemical composition of the LSCN were performed through
scanning electron microscopy (SUPRA 55 SAPPHIRE,
ZEISS, Germany). The XRD patterns of samples were
obtained by a Rigaku D/MAX-Ultima+ diffractometer oper-
ated at 40 kV and 40 mA with Co Kα radiation. The specific
surface areas and pore properties of samples were calculated
by Brunauer-Emmett-Teller (BET, WBL-8XX) and Barrett-
Joyner-Halenda. Specifically, the specific surface area was
determined by the BET multipoint method and degassed at
100°C for 120 minutes, of which the physical adsorption
method covered 6 points.
2.3. Ethanol Steam Reforming. The catalyst activity was eval-
uated in the ESR performance test system including the mass
flow controller, tube furnaces, quartz reactor, gas analyzers,
and data acquisition systems. The length of the quartz tube
is 50 cm, the outer diameter is 12 mm, and the inside diam-
300 400
600°C
650°C
eter is 10 mm. 0.2 g of the synthesized catalyst sample was
placed in a quartz tube reactor. The experimental setup for
ESR is shown in Figure 1.
The system was purged with N2 at a flow rate of 30 mL/
min for 15 minutes before each ESR test. The LSCN catalysts
were reduced under 300 mL/min of 10 vol% H2-N2 gas at
500°C for 90 min, followed by purging at the same tempera-
ture with 30 mL/min of N2 during 15 min. Subsequently,
nitrogen as a carrier gas delivered the vapor of the ethanol
aqueous solution mixture into the tube furnace reactor at a
flow rate of 30 mL/min. The volumetric concentrations of
H2, CO2, CH4, and CO in the gas products were measured
by the gas analyzer.
The conversion of ethanol and the yield of each compo-
nent in the gas product were estimated as
nout nCO + nCH4 + nCO2
C EtOH = = × 100%,
nin 2nEtOH
ð2Þ
ni
Yi = ,
nEtOH
where nin and nout are the molar amount of carbon in the
feed and the molar amount of carbon in the reformed gas,
respectively; CEtOH is the conversion of ethanol; Yi is the
yield of each gas component in the reformed gas (i = H2 ,
CO, CO2, and CH4); and nEtOH is the molar amount of eth-
anol in the feed.
3. Results and Discussion
3.1. Effect of Sr Doping on Catalytic Properties of La1-x
SrxCo0.5Ni0.5O3-δ. The catalytic performance of perovskite
International Journal of Energy Research 9

1.0

0.8

CO yield (mol/mol ethanol)

0.6

0.4

0.2

0.0
0 100 200 300 400

Time (Min)
3:1 5:1
4:1 6:1
(a)
1.2

1.0
CO2 yield (mol/mol ethanol)

0.8

0.6

0.4

0.2

0.0
0 100 200 300 400

Time (Min)
3:1 5:1
4:1 6:1
(b)

Figure 6: Continued.
10 International Journal of Energy Research

0.4

0.3

CH4 yield (mol/mol ethanol)

0.2

0.1

0.0
0 100 200 300 400

Time (Min)
3:1 5:1
4:1 6:1
(c)
6

5
H2 yield (mol/mol ethanol)

0
0 100 200 300 400

Time (Min)
3:1 5:1
4:1 6:1
(d)

Figure 6: Product yield of La0.1Sr0.9Co0.5Ni0.5O3-δ for ethanol steam reforming at different S/C ratio: (a) CO yield; (b) CO2 yield; (c) CH4
yield; (d) H2 yield.

is significantly affected by A-site doping. The results of eth-
anol conversion and product yields over La1-xSrxCo0.5-
Ni0.5O3-δ in the ESR are shown in Figure 2. The ethanol
conversion can reach 80%, 81%, 90%, and 92%, respectively,
when the ESR reaction is stable. As shown in Figure 3(a), the
highest ethanol conversion of 92% was achieved. The high
ethanol conversion of La0.1Sr0.9Co0.5Ni0.5O3-δ may be related
to the high activity caused by its higher specific surface area,
because the large specific surface area means that more
active sites are exposed [31]. From the BET data of the LSCN
samples, the doping of Sr causes changes in the specific sur-
face area, pore volume, and pore size of the catalyst, which in
International Journal of Energy Research
1.0
0.8
Ethanol conversion (100%)
0.6
0.4
0.2
0.0
0 100
3:1
4:1
Figure 7: Ethanol conversion of La0.1Sr0.9Co0.5Ni0.5O3-δ for ethanol steam reforming at different S/C ratio.
turn causes changes in its catalytic activity. The highest
activity of La0.1Sr0.9Co0.5Ni0.5O3-δ is represented by the
highest ethanol conversion and the highest yield of hydro-
gen. In general, the yield of carbon-containing gas products
(such as CO) is low, which is beneficial for the application of
this technology in the field of hydrogen fuel cells. In addi-
tion, the experimental results show that La0.1Sr0.9Co0.5-
Ni0.5O3-δ can produce 4.5 H2 mol/(C2H5OH mol).
The gas product selectivity of different samples is shown
in Figure 3(b). The catalyst samples with different strontium
content showed significant differences in ESR reaction. Sim-
ilar to the effect of Sr on the yield of gas products, it can be
observed that La0.1Sr0.9Co0.5Ni0.5O3-δ perovskite catalyst has
the highest H2 selectivity (71.29%), and the selectivity of CO,
CO2, and CH4 is 13.56%, 12.31%, and 2.86%, respectively.
Based on the above experimental results, it can be concluded
that the doping of Sr plays a positive role in the production
of high-quality hydrogen over the catalyst during the ESR
process. Compared with the catalyst without Sr doping, the
presence of strontium improves the ethanol conversion by
2%~12%. In addition, the CH4 selectivity of the Sr-
substituted samples was significantly decreased, which
means that the side reactions were inhibited in the ESR reac-
tion. In turn, the production of CO is reduced, which, to
some extent, prevents catalyst deactivation and carbon
deposition. La0.1Sr0.9Co0.5Ni0.5O3-δ has the highest hydrogen
yield (4.6 mol/(mol ethanol)) and ethanol conversion (92%),
so the La0.1Sr0.9Co0.5Ni0.5O3-δ was used as candidate for the
following research.
3.2. Effect of the Reaction Temperature of ESR. Temperature
is a crucial influencing factor for the catalytic reaction.
Figures 4 and 5 compare the curves of the ethanol conver-
11
1.0
0.8
0.6
0.4
0.2
0.0
200 300 400
Time (Min)
5:1
6:1
sion and the yield of each gas product of La0.1Sr0.9Co0.5
Ni0.5O3-δ at 500°C, 550°C, 600°C, and 650°C, respectively.
The results show that the hydrogen production of
La0.1Sr0.9Co0.5 Ni0.5O3-δ is directly proportional to the reac-
tion temperature and reaches the maximum at 600°C. The
ethanol steam reforming reaction is an endothermic reac-
tion, so the medium and high temperature environment is
conducive to the forward reaction [32]. In addition, too
low temperature will also lead to the complexity of the reac-
tion, which is shown by the increase of by-products. The
continuous increase of temperature, for example, will lead
to the decrease of hydrogen production, which may be
because the excessive temperature leads to the sintering
and carbon deposition of the catalyst, resulting in the
decrease of catalytic activity. At low temperatures such as
500°C, the presence of carbon-containing by-products such
as carbon monoxide, carbon dioxide, and methane in the
gas product indicates that a chain reaction has occurred in
the steam reforming reaction of ethanol. In this case, as
shown in equations (3) and (4), ethanol dehydrogenates to
acetaldehyde, hydrogen and acetone, carbon monoxide,
and hydrogen, respectively [33]. The occurrence of acetalde-
hyde decomposition reaction as shown in equation (5) may
be another reason for the increase of CH4 content. In addi-
tion, the reduction of hydrogen yield is caused by the
decomposition of ethylene into carbon (equation (6))
around 500°C, which also leads to the reduction or even
deactivation of the catalyst.
CH3 CH2 OH ⟶ CH3 CHO + H2 ð3Þ
2CH3 CH2 OH ⟶ CH3 COCH3 + CO + 3H2 ð4Þ
12 International Journal of Energy Research

1.0
1.0

0.8
0.8

CO2 yield (mol/mol ethanol)

CO yield (mol/mol ethanol)

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 100 200 300 400 0 100 200 300 400
Time (Min) Time (Min)
16.5 h−1 22.5 h−1 16.5 h−1 22.5 h−1
19.5 h−1 25.5 h−1 19.5 h−1 25.5 h−1

(a) (b)

0.3
4
CH4 yield (mol/mol ethanol)

H2 yield (mol/mol ethanol)

0.2

0.1

0.0 0
0 100 200 300 400
0 100 200 300 400
Time (min)
Time (min)
16.5 h−1 22.5 h−1
16.5 h−1 22.5 h−1 19.5 h−1 25.5 h−1
19.5 h−1 25.5 h−1

(c) (d)

Figure 8: Product yield of La0.1Sr0.9Co0.5Ni0.5O3-δ for ethanol steam reforming at different LHSV: (a) CO yield; (b) CO2 yield; (c) CH4 yield;
(d) H2 yield.

CH3 CHO ⟶ CH4 + CO
C2 H4 ⟶ 2C + 2H2
It can be observed that the yield of H2 is proportional to
temperature, while the yield of CH4 and CO is inversely pro-
portional to temperature. When the temperature is higher
than 600°C, the yield of H2 and CO2 show a downward
trend, while the yield of CO gradually increases. This means
that improving hydrogen selectivity and reducing the forma-
tion of by-products can be achieved by increasing the reac-
tion temperature. In addition, ESR is considered as a
carbon deposition reaction, and higher temperatures will
reduce carbon deposition [34], which also explains the phe-
nomenon as shown in Figure 5 that the catalytic perfor-
mance of La0.1Sr0.9Co0.5 Ni0.5O3-δ is the best at 600°C.
ð5Þ 3.3. Effect of the Ratio of S/C. The comparison of the gas
product yield and ethanol conversion of La0.1Sr0.9Co0.5-
ð6Þ Ni0.5O3-δ under different S/C conditions is shown in
Figures 6 and 7. As a general trend, when the ratio of S/C
was increased to 4 : 1, the content of gas products such as
hydrogen, carbon dioxide, carbon monoxide, and methane
increased significantly, which indicates that an appropriate
S/C ratio is conducive to promote the overall ESR reaction
[35]. Figure 6(a) shows CO flow as function of S/C ratio.
With the increase of the ratio of water to alcohol, the
amount of CO production increased firstly and then
decreased. Thus, it shows that the production of CO can
be inhibited. The production of CO is stabilized at 0.7 mol/
mol ethanol.
On the other hand, if the water content increases to a
certain extent, its influence on the chemical balance will be
International Journal of Energy Research 13

1.0

0.8

Ethanol conversion (100%)

0.6

1.0

0.4 0.8

0.6

0.4
0.2 0.2

0.0
1 2 3 4

0.0
0 100 200 300 400
Time (min)

16.5 h−1 22.5 h−1

19.5 h−1 25.5 h−1

Figure 9: Ethanol conversion of La0.1Sr0.9Co0.5Ni0.5O3-δ for ethanol steam reforming at different LHSV.

4.5
1.0
4.0
1.0
3.5
0.8
Product yield (mol/mol ethanol)

Ethanol conversion (100%)

Ethanol conversion (100%)

3.0

2.5 0.8 0.6

2.0
0.4
1.5
0.6
1.0
0.2

0.5

0.0 0.4 0.0

0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Time-on-stream (h) Time (h)

CO H2 La0.1Sr0.9Co0.5Ni0.5O3-𝛿
CO2 Ethanol conversion LaCo0.5Ni0.5O3-𝛿
CH4

(a) (b)

Figure 10: (a) Stability test of the La0.1Sr0.9Co0.5Ni0.5O3-δ perovskite structured sample at optimal conditions: (yellow diamond) CO; (red
circle) CO2; (blue up-pointing triangle) CH4; (green down-pointing triangle) H2; (gray square) ethanol conversion). (b) Ethanol
conversions of La0.1Sr0.9Co0.5Ni0.5O3-δ and LaCo0.5Ni0.5O3-δ.

weakened and the ESR reaction will need to be supplied with 3.4. Effect of the LHSV. The comparison of the gas product
more energy. In order to increase the H2 production rate as yield and ethanol conversion of La0.1Sr0.9Co0.5Ni0.5O3-δ
much as possible, it is essential to increase the H2 production under different LHSV conditions is shown in Figures 8
rate by ensuring a sufficient supply of raw water while avoid- and 9. It can be seen that when the LHSV is increased
ing excessive water to promote the dehydration and decom- from 16.5 h-1 to 19.5 h-1, the reaction products (CO, CO2,
position of ethanol. Therefore, increasing S/C ratio is an CH4, and H2) are significantly increased; at this time, the
important way to inhibit CO yield. In conclusion, the S/C yield of H2 is about 4.7 mol/(mol ethanol), and the prod-
ratio of 5 : 1 was taken as the best reaction condition of uct yields of CO, CO2, and CH4 are 0.88 mol/(mol etha-
La0.1Sr0.9Co0.5Ni0.5O3-δ in the following experiments. nol), 0.92 mol/(mol ethanol), and 0.24 mol/(mol ethanol),
14 International Journal of Energy Research

La0.1Sr0.9Co0.5Ni0.5O3-𝛿
La0.1Sr0.9Co0.5Ni0.5O3-𝛿

Intensity (A.U.)
Intensity (A.U.)

La0.5Sr0.5Co0.5Ni0.5O3-𝛿

La0.5Sr0.5Co0.5Ni0.5O3-𝛿
La0.9Sr0.1Co0.5Ni0.5O3-𝛿

La0.9Sr0.1Co0.5Ni0.5O3-𝛿
perovskite PDF#82–0228

32 33 34 35 36 37 38
10 20 30 40 50 60 70 80 90
Two–theta (degree) Two–theta (degree)

(a) (b)

Figure 11: XRD patterns of (a) La1-xSrxCo0.5Ni0.5O3-δ, (b) along with the magnified patterns for 2θ from 32° to 38°.

(a) (b)

Figure 12: SEM images of La0.1Sr0.9Ni0.5Co0.5O3-δ catalysts: (a) fresh La0.1Sr0.9Ni0.5Co0.5O3-δ sample; (b) La0.1Sr0.9Ni0.5Co0.5O3-δ sample
reduced by H2.

respectively. With the increase of LHSV, the ethanol conver-

sion was increased and then decreased. The ethanol conver- Table 1: SBET, pore volume, and pore size of the fresh samples and
sion reached the highest value of 19.5 h-1 and the ethanol samples after hydrogen reduction.
conversion was 98.7%. According to the chemical equilibrium SBET Pore volume Pore size
movement principle, an increase of the gas reaction pressure is Sample
(m2/g) (mL/g) (nm)
beneficial to the direction of the decrease of the number of
LaNi0.5Co0.5O3-δ 1.8846 0.0044 9.8243
moles of the ESR reaction. This phenomenon can be under-
stood as a certain number of active sites of the catalyst are a La0.9Sr0.1Ni0.5Co0.5O3-δ 2.7040 0.0071 10.5030
certain number, which is gradually from the under-load state La0.5Sr0.5Ni0.5Co0.5O3-δ 2.4267 0.0084 13.8460
to the process of full-load state. Therefore, the increase of La0.1Sr0.9Ni0.5Co0.5O3-δ 3.7714 0.0127 13.4698
LHSV to a certain value is not conducive to the conversion La0.1Sr0.9Ni0.5Co0.5O3-δ
7.5648 0.0017 13.8460
of ethanol and water. (H2 reduction)
La0.1Sr0.9Ni0.5Co0.5O3-δ
6.0085 0.0099 13.6645
3.5. Stability Test. Excellent thermal stability, i.e., service (40 h)
life, is the key to the practical application of the catalyst
in ESR. In this study, the stability test experiment of
La0.1Sr0.9Co0.5Ni0.5O3-δ was carried out for up to 40 h is 600°C, the optimal S/C ratio is 5 : 1, and the optimal
under the optimal conditions. Based on these experiments, LHSV is 19.5 h-1. As shown in Figure 10(a), the deactiva-
it can be obtained that the optimal reforming temperature tion of the La0.1Sr0.9Co0.5Ni0.5O3-δ catalyst sample after
International Journal of Energy Research 15

1.20×10−3

16

14 9.00×10−4

dV/dD (ml.nm−1.g−1)
Adsorbed Capacity (ml/g)

12

10 6.00×10−4

3.00×10−4
6

4
0.00
2

0
0 20 40 60 80 100 120 140 160
0.0 0.2 0.4 0.6 0.8 1.0
Pore Diameter (nm)
Relative Pressure (P/P0)

(a) (b)

Figure 13: (a) The adsorption isotherm of La1-xSrxCo0.5Ni0.5O3-δ perovskite oxide catalysts. (b) Pore size distribution of La1-xSrxCo0.5Ni0.5O3-δ
perovskite oxide catalysts.

40 hours of ethanol steam reforming reaction was not Figure 11(b)), indicating that the performance of perov-
observed. The ethanol conversion was finally stabilized at skite catalyst samples becomes better. The broadening
98%, and the yield of each gas product did not drop sig- degree of characteristic peak in XRD pattern is inversely
nificantly. The excellent thermal stability is due to the proportional to the crystal size. In other words, when the
solid cubic structure of perovskite-type metal oxides. characteristic peak is sharper, the crystal structure will be bet-
In addition, the ethanol conversion of La0.1Sr0.9Co0.5- ter. Figure 12 shows a comparison of SEM images of fresh
Ni0.5O3-δ and LaCo0.5Ni0.5O3-δ in ESR was compared at La0.1Sr0.9Ni0.5Co0.5O3-δ sample powders and La0.1Sr0.9Ni0.5-
600°C, and the results are shown in Figure 10(b). It can be Co0.5O3-δ reduced by H2. It can be observed that the mor-
significantly observed that the ethanol conversion of the phology of fresh La0.1Sr0.9Ni0.5Co0.5O3-δ samples is porous
La0.1Sr0.9Co0.5Ni0.5O3-δ catalyst is higher than that of the and rough. As shown in Figure 12, the fresh La0.1Sr0.9Ni0.5-
LaCo0.5Ni0.5O3-δ. The ethanol conversion of LaCo0.5- Co0.5O3-δ and La0.1Sr0.9Ni0.5Co0.5O3-δ reduced by H2 showed
Ni0.5O3-δ is only 89.4%, while the ethanol conversion of similar surface morphology, but the La0.1Sr0.9Ni0.5Co0.5O3-δ
La0.1Sr0.9Co0.5Ni0.5O3-δ is close to complete conversion. As sample reduced by hydrogen showed a denser porous net-
shown by the BET results we tested, the difference in perfor- work structure. However, the denser surface structure of
mance between the two is also reflected in the difference in fresh La0.1Sr0.9Ni0.5Co0.5O3-δ results in a smaller specific
their BET. A catalyst with a larger specific surface area will surface area. These results can be confirmed by XRD anal-
show better catalytic activity. The addition of strontium ysis and SEM observation. Therefore, the La0.1Sr0.9Ni0.5-
increases the specific surface area of the catalyst, thus expos- Co0.5O3-δ perovskite showed a better crystal structure.
ing more active sites. It is concluded that La0.1Sr0.9Co0.5- Table 1 displays the specific surface area, pore volume,
Ni0.5O3-δ has excellent catalytic performance and can and pore size of the fresh samples and samples after
produce relatively good quality H2. hydrogen reduction. The specific surface area of the fresh
samples is smaller because they are all obtained by high
3.6. Catalyst Characterizations. The XRD pattern of the temperature calcination [37]. The small specific area is a
La1-xSrxCo0.5Ni0.5O3-δ (x = 0:1, 0.5, 0.9) perovskite samples characteristic of perovskite powders. Among these perov-
are shown in Figure 11. The strong peaks occurred at 27°, skites with different Sr doping amounts, La0.1Sr0.9Ni0.5-
38.6°, 55.7°, and 70.2° (JCPDS No. 82-0228) [36], which Co0.5O3-δ obtained the maximum specific surface area of
indicated that the lanthanide cobalt-based perovskite metal 3.7714 m2/g. The specific surface area, pore volume, and pore
oxide has been successfully synthesized. The phase is basi- diameter of La0.1Sr0.9Ni0.5Co0.5O3-δ after hydrogen reduction
cally the same as perovskite, except for the newly formed were significantly increased, which were 7.5648 m2/g,
secondary phase LSCN. In addition, there are sharp char- 0.0017 mL/g, and 13.8460 nm, respectively. After 40 hours
acteristic peaks unique to perovskite on the catalyst sam- of continuous experiments, the specific surface area, pore
ple, indicating that the crystal structure of the prepared volume, and pore diameter of La0.1Sr0.9Ni0.5Co0.5O3-δ remain
catalyst sample is intact. In particular, it can be found that unchanged; this also proves that La0.1Sr0.9Ni0.5Co0.5O3-δ
as the doping amount of Sr element increases, the charac- shown in Figure 12 has excellent thermal stability.
teristic peak shifts to a low angle, and the peak shows a Figures 13(a) and 13(b) show the adsorption isotherm
trend of sharper and narrower peak width (as shown in and pore size distribution of La1-xSrxNi0.5Co0.5O3-δ (y = 0,
16 International Journal of Energy Research

SEM O Co

Ni Sr La

Figure 14: EDS mapping image of La0.1Sr0.9Co0.5Ni0.5O3-δ catalyst.

0.1, 0.5, 0.9) perovskite catalysts, respectively. The synthe- Table 2: Elemental composition of synthesized La0.1Sr0.9Co0.5Ni0.5O3-δ
catalyst.
sized catalysts exhibit the typical type III isotherms of perov-
skite as exhibited in Figure 13(a). It can be seen from the Elements Mass percentage (%) Atomic percentage (%)
adsorption isotherm curve that the content of Sr element is
La 9.454 2.035
generally positively correlated with the adsorption capacity
of perovskite samples, especially the adsorption capacity of Sr 44.859 18.826
La0.1Sr0.9Ni0.5Co0.5O3-δ after H2 reduction is the strongest. Ni 13.267 10.078
When P0 = 1:038, the La0.1Sr0.9Ni0.5Co0.5O3-δ treated with Co 12.945 9.793
hydrogen reduction can reach 16.18 mL/g, and the adsorp- O 19.474 59.267
tion capacity is increased by 45% compared with the
La0.1Sr0.9Ni0.5Co0.5O3-δ before reduction. In addition, the
adsorption capacity of the sample (9.51 mL/g, P0 = 1:039) 4. Conclusions
was also the highest compared with the other samples in
the 40 h stability test. Figure 13(a) also shows that the The present work shows that La1-xSrxCo0.5Ni0.5O3-δ (x = 0,
adsorption capacities of LaNi0.5Co0.5O3-δ, La0.9Sr0.1Ni0.5- 0.1, 0.5, 0.9) perovskite is a promising precursor of ESR
Co0.5O3-δ, and La0.5Sr0.5Ni0.5Co0.5O3-δ were 2.77 mL/g hydrogen production catalyst. The physicochemical proper-
(P0 = 1:015), 4.68 mL/g (P0 = 1:043), and 5.48 mL/g ties of the synthesized catalyst samples were studied by XRD,
SEM, EDS, and BET. In addition, the effects of experimental
(P0 = 1:045), respectively. The pore size distribution of the
operating parameters on the catalytic ethanol reforming
La1-xSrxNi0.5Co0.5O3-δ perovskite catalysts is mainly concen-
reaction for hydrogen production are described in detail.
trated in the 0-10 nm range (as shown in Figure 13(b)).
The main conclusions are as follows:
The pore size of La0.1Sr0.9Ni0.5Co0.5O3-δ reduced by H2 is
1:35 × 10−3 (mL·nm-1·g-1), which means that the La0.1Sr0.9- (1) The addition of Sr at A-site changed the characteris-
Ni0.5Co0.5O3-δ perovskite catalyst will have better stability tics of the catalyst and improved its catalytic perfor-
and catalytic ability in the ethanol reforming process. mance, which showed that the pore volume and pore
Figure 14 and Table 2 display the EDS analysis results of diameter of La1-xSrxCo0.5Ni0.5O3-δ perovskite gradu-
the catalyst sample La0.1Sr0.9Ni0.5Co0.5O3-δ with the best cat- ally increased with the increase of strontium, and the
alytic effect. In the selected mapping area, it can be con- reduction of hydrogen further promotes this trend
firmed that all the elements in the catalyst are La, Sr, Co,
Ni, and O. According to the element statistics, La: Sr: Co: (2) XRD confirmed that the substitution of Sr element
Ni is in good agreement with the theoretical value of will increase the number of oxygen vacancies in
1 : 9 : 5 : 5. perovskite metal oxides, and the oxygen vacancies
International Journal of Energy Research
on the surface can adsorb oxygen-containing species,
which will promote the contact between the reac-
tants and the catalyst. The specific surface area of
porous and rough La0.1Sr0.9Ni0.5Co0.5O3-δ samples
is the largest (3.7714 m2/g) among perovskite with
different Sr doping amount
(3) The optimal ESR operating conditions for La0.1Sr0.9-
Co0.5Ni0.5O3-δ are determined: the optimal reaction
temperature is 600°C, the optimal S/C is 5 : 1, and
the optimal LHSV is 19.5 h-1. After 40 hours of sta-
bility testing under optimal operating conditions,
the deactivation of La0.1Sr0.9Co0.5Ni0.5O3-δ is not
observed, which is attributed to the stability of its
surface properties (such as specific surface area, pore
volume, pore size) and the stable structure of perov-
skite. In the next experiment, we will try to reduce
the working temperature of the catalyst by loading
the support and doping elements, which will make
it more practical
Data Availability
The data used to support the findings of this study are avail-
able from the corresponding author upon request.
Conflicts of Interest
The author(s) declare(s) that they have no conflicts of
interest.
Acknowledgments
This work was supported by the China Postdoctoral Science
Foundation (No. 2019M651094) and the Science and Tech-
nology Innovation Foundation of Dalian (2021JJ11CG004).
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