Promoting effects of lanthanum oxide on the NiO/CeO2 catalyst for hydrogen production by autothermal reforming of ethanol

Article abstract of DOI:10.1016/j.catcom.2018.01.024

Promoting effects of Lanthanum oxide on the NiO/CeO₂ catalyst for hydrogen production by autothermal reforming of ethanol were investigated. The effects of La increased the specific surface area, stabilized the NiO phase and led to the high dis

Full text of DOI:10.1016/j.catcom.2018.01.024

CatalysisCommunications108(2018)12–16
Contents lists available at ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short communication
Promoting effects of lanthanum oxide on the NiO/CeO2 catalyst for
hydrogen production by autothermal reforming of ethanol
⁎
Zhiwei Xuea,b,c,d, Yuesong Shena,b,c, , Peiwen Lid, Youchun Pana,b,c, Junjie Lia, Zhiliang Fenga,
Yu Zhanga,b,c, Yanwei Zenga, Youlin Liua,b,c, Shemin Zhua,b,c
a
College of Materials Science and Engineering, The University of Arizona, Tucson, AZ 85721-0119, USA
Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, The University of Arizona, Tucson, AZ 85721-0119, USA
Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 210009, China
Department of Aerospace and Mechanical Engineering, The University of Arizona, Tucson, AZ 85721-0119, USA
b
c
d
A R T I C L E I N F O
A B S T R A C T
Keywords:
Promoting effects
Lanthanum
Promoting effects of Lanthanum oxide on the NiO/CeO2 catalyst for hydrogen production by autothermal re-
forming of ethanol were investigated. The effects of La increased the specific surface area, stabilized the NiO
phase and led to the high dispersion of Ni in active LaNiO3 phase. The carrier CeO2 provided big specific surface
area for effective EATR reaction, promoted the H2 production by accelerating the oxygen migration in the
catalyst surface via the Ce4+ ↔ Ce3+ transformation. Consequently, the optimized Ni1La1Oy/10CeO2 catalyst
achieved 100% XEtOH, 69.3% SH2 at 600 °C and high stability at 550 °C.
CeO2
Hydrogen production
Ni-based catalyst
Autothermal reforming
1. Introduction
metal (such as Rh [12], Ru [13] and Pt [8]) catalysts are highly active
and exhibit prominent anti-coke ability during reforming reactions.
Energy shortage and environment pollution are accelerating the
evolutions of clean, high efficient and renewable energies [1]. Hy-
drogen energy is one of the most promising sustainable energies [2,3].
Particularly, the increasing application of fuel cells [4] requires highly-
efficient and -convenient supply of H2. Catalytic reforming of organic
compounds for H2 production has attracted increasing attention [5,6],
and the approach of autothermal reforming (ATR as abbreviation) [7] is
becoming popular because it combines the advantages of steam re-
forming (SR) [8] and partical oxidation (PO) [9]. Therefore, developing
the ATR technology is necessary for advancing the hydrogen economy.
Ethanol (EtOH) is a potential hydrogen source because of its ad-
vantages such as feasible thermodynamic decomposition, cheap, re-
newable, transportable and low toxicity [10,11]. Eq. (1) displays the
chemical equation for ATR of EtOH (EATR). Approximate ATR process
can be achieved by adjusting the molar ratio of reactants. When the
value of δ is set as 0.5, 5 mol H2 could be produced from 1 mol EtOH,
and ΔH equals to −68.06 kJ/mol. Thus, the reaction requires no extra
energy from the external environment.
However, high cost of noble-metal materials inhibits their application.
Herein, non-noble metals (such as Ni [10,14], Co [15,16], Cu [17]) are
becoming more and more popular because of their low cost and sa-
tisfying properties. Typically, Ni and NiO possess excellent abilities for
CeC, CeH and CeO bonds cleavage, and dehydrogenation [18].
However, Ni-based catalysts can be easily deactivated by coke deposi-
tion, which constrains their further application [19]. Thus, it is neces-
sary to design new catalysts to overcome coke deposition. In our pre-
vious work, La not only increased the activity of Ni-based catalyst, but
prolonged its lifetime [20]. Besides, LaNiO3, formed by the interaction
between La2O3 and NiO, favored the reactions of dehydrogenation,
decomposition of hydrocarbons and water gas shift (WGS) [21], which
are essential for ATR reactions. Furthermore, LaNiO3 promotes the
dispersion of Ni, and provides more active sites than the single NiO,
which is crucial for an efficient nickel-based catalyst [19]. In addition,
ceria is a considerable material for reforming catalysts because of its
redox ability, oxygen storage capacity (OSC) [22], and Ce3+ ↔ Ce4+
transformation [23]. CeO2 can improve the activity of WGS reaction,
which is a significant step of ATR [7]. Mudiyanselage et al. [13] in-
vestigated reactions of ethanol over CeO2 and Ru/CeO2. The main re-
actions of ethanol on CeO2 were re-combinative desorption of ethanol,
dehydrogenation to acetaldehyde and dehydration to ethylene. The
presence of Ru considerably modified the reaction of ceria towards
kJ
C2H5OH + (3 − 2δ)H2O + δO2 → 2CO2 + (6 − 2δ)H2
∆H ≈ 0
mol
(1)
The reforming catalyst is one of the key factors of ATR. The noble
⁎
Corresponding author at: No.5 Xinmofan Road, College of Materials Science and Engineering, Nanjing Tech University, 210009 Nanjing, China.
E-mail address: shenyuesong@njtech.edu.cn (Y. Shen).
https://doi.org/10.1016/j.catcom.2018.01.024
Received 5 October 2017; Received in revised form 19 December 2017; Accepted 21 January 2018
1566-7367/©2018ElsevierB.V.Allrightsreserved.

Z. Xue et al.
CatalysisCommunications108(2018)12–16
and 74.8% SH2 at 550 °C, while XEtOH of Ni1La1Oy/10CeO2 catalyst was
slightly lower. The hydrogen in the ethanol and H2O was co-converted
in molecular H2. However, SH2 of the Ni2La2Oy/10CeO2 catalyst de-
clined from 74.8% to 68.8% when increasing the temperature from 550
to 600 °C. The result indicated that undesired deactivation happened in
the Ni2La2Oy/10CeO2 catalyst when the reaction temperature was high.
Specially, SH2 of Ni1La1Oy/10CeO2 catalyst kept continuous growth at
the entire test and reached 69.3% at 600 °C, indicating that Ni1La1Oy/
10CeO2 was be relatively stable during EATR. Similar tendency was
concluded from the results of SCO2 displayed in Fig. dramatically went
up by increasing the concentration of Ni, while the addition of La also
promoted the XEtOH and SH2. In addition, the H2 yields of catalysts NiO/
10CeO2, La2O3/10CeO2 and Ni1La1Oy/10CeO2 shown in Fig. S9 further
proved the promoting effect of La. Therefore, La was an effective pro-
moter in the reforming catalyst.
Although the Ni2La2Oy/10CeO2 catalyst exhibited high XEtOH and
SH2, the undesired deactivation might make it inapplicable. Herein, it is
necessary to measure the stability of Ni1La1Oy/10CeO2 and Ni2La2Oy/
10CeO2 catalysts.
The stability test was carried at 550 °C for 50 h, and the results were
shown in Fig. S2. The Ni1La1Oy/10CeO2 catalyst exhibited high stabi-
lity over the entire 50 h, whereas XEtOH of the Ni2La2Oy/10CeO2 cata-
lyst declined from 100% to 86% after the test. In addition, the carbon
balance (the calculation method was described in Methods in supple-
mentary materials) of the Ni1La1Oy/10CeO2 and Ni2La2Oy/10CeO2
catalysts at different reaction temperatures were calculated and shown
in Table S1. At the temperature lower than 600 °C, the carbon balance
of the Ni2La2Oy/10CeO2 catalyst was higher than that of the Ni1La1Oy/
10CeO2 catalyst. However, the Ni1La1Oy/10CeO2 catalyst obtained the
carbon balance of 85% at 600 °C, which was 10.1% higher than that of
Ni2La2Oy/10CeO2 catalyst. The high carbon balance made the coke
hardly deposited on the surface of the catalyst. The Ni2La2Oy/10CeO2
catalyst was indeed deactivated during the EATR reaction, and the
deactivation might be caused by the excess Ni in the catalyst. Therefore,
the Ni1La1Oy/10CeO2 was the optimal catalyst with high activity, se-
lectivity and stability for H2 production.
The overall performance of the Ni1La1Oy/10CeO2 catalyst was
shown in Fig. S3. The Ni1La1Oy/10CeO2 catalyst exhibited relatively
low selectivity towards the products of CO and CH4. As mentioned by
Rupali R. Davda [24], the products of EATR reaction with very low
levels of CO and CH4 was directly suitable for the application of fuel
cells. In addition, H2 selectivity of the Ni1La1Oy/10CeO2 catalyst tested
under different S/C and O/C feed ratios were investigated, and the data
and its description were shown in Fig. S7. The result indicated that
more H2O in reactants provided more hydrogen atoms, while the ap-
propriate amount of oxygen provided the heat for the steam reforming.
The highest SH2 of 73.8% was obtained when S/C = 4, O/C = 0.5.
Therefore, the Ni1La1Oy/10CeO2 catalyst was a potential catalyst for
producing the fuel-cell-grade hydrogen.
Fig. 1. The catalytic performance of the NiaLabOy/10CeO2 catalysts. A. EtOH conversion
rate of the catalysts at reaction temperature from 400 to 600 °C. B. H2 selectivity of the
catalysts at reaction temperature from 400 to 600 °C. (H2O/EtOH = 3:1, O2/
EtOH = 0.5:1, GHSV = 20,000 h−1).
ethanol, and switched the desorption products to CO, CO2, CH4 and H2.
Active components were significant in changing selectivities of the
catalyst with CeO2 as its carrier.
In this work, with the aim at enhancing the stability of Ni-based
2.2. Characterizations
catalyst and improving its H2 production, we developed
a new
NiaLabOy/10CeO2 catalyst with La as its co-catalyst and CeO2 as its
carrier. The effects of lanthanum oxide on the NiaLabOy/10CeO2 cata-
lyst were investigated. The experimental section was described in the
supplementary materials.
2.2.1. X-ray diffraction
The XRD patterns of the prepared catalysts were shown in Fig. S4.
The main characteristic peaks marked by o at the2θ angles of 28.3,
32.9, 41.2 and 56° were corresponding to the phase of fluorite type
CeO2 (PDF card 65-2975). The peaks marked by x with very low in-
tensity at 2θ angles of 37.3, 43.3 and 62.9° were corresponding to the
phase of NiO. However, the La was undetectable from the XRD patterns.
The result indicated that La was highly dispersed in the catalyst.
Besides, the three major XRD diffraction peaks of LaNiO3 phase at 2θ
angles of 32.9, 47.4 and 58.8° were overlapped by the diffraction peaks
of CeO2 phase, which suggested that LaNiO3 might be a possible
structure formed by La2O3 and NiO. In addition, the 2θ angles of CeO2
phase slightly shifted towards the low angle (shown in Fig. S4-B), which
might be caused by the existence of the LaNiO3 phase, or the
2. Results and discussion
2.1. Catalytic performance
The study was started by evaluating the catalytic performance of
NiaLabOy/10CeO2 catalysts. As shown in Fig. 1, the XEtOH was markedly
affected by Ni/La/Ce molar ratios. On the one hand, both the XEtOH and
SH2 went up with the increasing amount of NiLaOy. The Ni2La2Oy/
10CeO2 catalyst achieved the highest performance with 100% XEtOH
13

Z. Xue et al.
CatalysisCommunications108(2018)12–16
Table 1
Textural property of prepared catalysts.
Sample
BET surface
Average pore
diameter/(Å)
Pore volume/
area/(m2 g−1
)
(cm3 g−1
)
Ni0.5La0.5Oy/
41
160.5
0.1599
10CeO2
Ni0.5La1Oy/10CeO2
Ni1La0.5Oy/10CeO2
Ni1La1Oy/10CeO2
Ni2La2Oy/10CeO2
43
33
47
41
139.1
186.1
139.1
139.1
0.1743
0.1129
0.1688
0.1718
incorporation of La3+ (0.11 nm) and Ni2+ (0.069 nm) into the lattice
of CeO2[25]. The results of Raman in Fig. S8 also proved the in-
corporation. Both the interactions of La with NiO and CeO2 were pro-
motional for H2 production via EATR [20,21,26]. Therefore, La not only
highly dispersed in the catalyst but could promote the H2 production.
2.2.2. Texture property
The BET surface area, average pore diameter and pore volume of the
prepared catalysts were shown in Table 1. All catalysts possessed re-
latively high specific surface area, which was contributed by the carrier
CeO2. The surface area of the Ni1La1Oy/10CeO2 catalyst was
47 m2 g−1, which was 6 m2 g−1 larger than both Ni0.5La0.5Oy/10CeO2
and Ni2La2Oy/10CeO2 catalysts. The trend in BET surface area when
increasing the NiLaOy loading was parabolic. In addition, the surface
area of Ni0.5La1Oy/10CeO2 was slightly larger than that of Ni0.5La0.5Oy/
10CeO2, whereas the surface of surface area of Ni1La0.5Oy/10CeO2 was
markedly lower than that of Ni0.5La0.5Oy/10CeO2. The results indicated
that the addition of La could increase the specific surface area of the
catalyst, whereas the addition of Ni could dramatically decrease the
specific surface area. The phenomenon was mainly caused by the ionic
radius of Ni and La, where Ni2+ with small radius of 0.069 nm can
easily enter the holes in the catalyst and La3+ with big radius of
0.11 nm can expand the structure of CeO2. Therefore, both the effects of
La and CeO2 led to the high specific surface area. Furthermore, the
Ni1La1Oy/10CeO2 catalyst possessed the biggest specific surface area
(similar to BET areas of CeO2 and Ru/CeO2[13]), which suggested that
big specific surface area might enhance the stability of the catalyst.
Fig. 3. H2-TPR results of the prepared catalysts.
suggested that the coke deposition contained multiwall carbon nano-
tubes. Herein, coke deposition caused the deactivation of the Ni2La2Oy/
10CeO2 catalyst. The micro-morphology of the Ni1La1Oy/10CeO2 cat-
alyst after normal EATR test (Fig. S5-A-2) showed no obvious coke
deposition in the surface of the catalyst, which indicating that the
catalyst possessed high anti-coke ability during EATR reaction. The
high concentration of NiO in catalysts might be the cause of coke de-
position, since big NiO particles could be easily deactivated [27]. As
shown in Fig. S5, the surface of the fresh Ni2La2Oy/10CeO2 catalyst had
many particles with the size ~1 μm, which might be the agglomeration
of NiO. Differently, there were rare particles in the surface of the
Ni1La1Oy/10CeO2 catalyst. Consequently, an appropriate concentration
of NiO in the catalyst could enhance its anti-coke ability.
2.2.4. H2-TPR of catalysts
The redox properties of the prepared catalysts were investigated by
H2-TPR. According to the profiles in Fig. 3, two obvious hydrogen
consumption peaks were observed at 200–400 °C. The first peak was
corresponding to the reduction of surface NiO, and the second peak was
seemingly ascribed to the reduction of surface oxygen in Ce4+-O-
Ce4+[28]. However, the variation of the second peak indicated that the
concentration of La in the catalysts dramatically affected the second
peak [29]. Herein, the inconspicuous peak at ~430 °C was caused by
the reduction of the surface oxygen in Ce4+-O-Ce4+. Specially, the
2.2.3. SEM graphs of the fresh and used catalysts
As discussed above, the deactivation of the Ni2La2Oy/10CeO2 cat-
alyst might be cause by the coke deposition during EATR reaction. To
confirm the hypothesis, the micro-morphology of the Ni2La2Oy/10CeO2
catalyst after deactivation was observed by SEM. According to the SEM
graph in Fig. 2, its surface was covered with cotton-shaped substances
with diameter of 20–100 nm. The morphology of the substances
Fig. 2. The micro-morphologies of the used Ni1La1Oy/10CeO2 catalyst (left) and the used Ni2La2Oy/10CeO2 catalyst (right).
14

Z. Xue et al.
CatalysisCommunications108(2018)12–16
indicated that the Ce4+ ↔ Ce3+ transformation in the catalyst was
active, which could promote the oxygen migration in the surface of the
catalyst and further improve the H2 production via EATR.
Fig. 4B showed the XPS spectra in Ni 2p and La 3d region. The most
intense Ni 2p3/2 peak of fresh catalyst appeared at BE around 854.7 eV,
while Ni 2p1/2 peak appeared at 871.9 eV. the two peaks were char-
acteristics of Ni2+ and Ni3+ ions in an oxidic environment, respectively
[32]. A satellite peak appeared at BE of 863.7 eV was caused by the rise
of Ni3+ ions, which suggested the formation of perovskite-type
LaNiO3[33] and the existence of Ni3+ ↔ Ni2+ transformation. The
existence of Ni3+ ↔ Ni2+ transformation revealed that the NiO phase
was relatively stable in the catalyst. In La 3d region, the peak of La 3d3/
2 located at BE of 850.1 eV, while peaks of La 3d5/2 located at BE of 838
and 833.1 eV. These peaks were corresponding to La3+ ions in an
oxidic environment [34]. Additionally, the difference of the XPS spectra
in O 1s region (Fig. S6) between the fresh and used Ni1La1Oy/10CeO2
catalysts demonstrated the LaeO bond was stable in the catalyst [35].
3. Conclusions
The technological evolutions for H2 production are emergent in our
society for solving the global energy and environment problems. With
the aim at enhancing the stability of Ni-based reforming catalyst and
improving its H2 production, a series of NiaLabOy/10CeO2 catalysts
were designed and investigated in this work. The results indicated that
the mass amount of NiaLabOy and the amount of Ni and La in the cat-
alysts markedly affected the catalytic performance. Among the pre-
pared catalysts, the Ni1La1Oy/10CeO2 achieved the optimized perfor-
mance with 100% XEtOH, 69.3% SH2 and high stability at 550 °C. The
effects of La increased the specific surface area, stabilized the NiO phase
and led to the formation of active LaNiO3 phase by the strong inter-
action between La and NiO. The carrier CeO2 provided big specific
surface area for effective EATR reaction, promoted the H2 production
by accelerating the oxygen migration in the catalyst surface via the
Ce4+ ↔ Ce3+ transformation. Furthermore, the NiO itself in the
Ni1La1Oy/10CeO2 catalyst was active and stable, and an appropriate
concentration of NiO in the catalyst could enhance its anti-coke ability.
This work paves the way towards new reforming catalysts for H2 pro-
duction.
Fig. 4. The XPS spectra of the fresh and used Ni1La1Oy/10CeO2 catalyst: A, the XPS
spectra in Ce 3d region; B, the XPS spectra in Ni 2p and La 3d region.
Acknowledgements
Ni0.5La1Oy/10CeO2 catalyst exhibited only one H2 consumption peak at
200–400 °C, which indicated that the small amount of Ni could easily
dope and disperse into La2O3 or CeO2, and formed new structures with
relatively high stability. Therefore, the reduction of Ni2+ became dif-
ficult at the low temperature (~250 °C), which leads to the only one H2
consumption peak at 200–400 °C. In addition, the peak at ~730 °C was
ascribed to the reduction of bulk CeO2[29]. Therefore, La and CeO2
made the catalyst possess high OSC and redox property, which were
essential for ATR reactions. Furthermore, the addition of La stabilized
the NiO by the formation of the LaNiO3 phase.
We acknowledge the financial supports of the National Key
Research and Development Program of China (No. 2016YFC0205500),
the National Natural Science Foundation of China (51772149), and the
Priority Academic Program Development of Jiangsu Higher Education
Institutions (PAPD).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.catcom.2018.01.024.
2.2.5. XPS analysis of the Ni1La1Oy/10CeO2
References
The surface atomic chemical states of the Ni1La1Oy/10CeO2 catalyst
before and after stability test were analyzed by X-ray photoelectron
spectroscopy (XPS). The curves were fitted using the software ‘XPS
PEAK’ to obtain characteristic peaks of certain atoms. The XPS spectra
in Ce 3d region were displayed in Fig. 4A. The XPS peaks at BE of 902.5
and 883.7 eV were ascribed to Ce3+, while other peaks were referred to
[1] J. Lelieveld, J.S. Evans, M. Fnais, D. Giannadaki, A. Pozzer, The contribution of
outdoor air pollution sources to premature mortality on a global scale, Nature 525
(2015) 367–371.
[2] S.-F. Weng, Y.-H. Wang, C.-S. Lee, Autothermal steam reforming of ethanol over
La2Ce2−xRuxO7 (x = 0–0.35) catalyst for hydrogen production, Appl. Catal. B
Environ. 134 (2013) 359–366.
[3] J. Xuan, M.K.H. Leung, D.Y.C. Leung, M. Ni, A review of biomass-derived fuel
processors for fuel cell systems, Renew. Sust. Energ. Rev. 13 (2009) 1301–1313.
[4] M. Lefèvre, E. Proietti, F. Jaouen, J.-P. Dodelet, Iron-based catalysts with improved
oxygen reduction activity in polymer electrolyte fuel cells, Science 324 (2009)
71–74.
[5] L. Lin, W. Zhou, R. Gao, S. Yao, X. Zhang, W. Xu, S. Zheng, Z. Jiang, Q. Yu, Y.-W. Li,
C. Shi, X.-D. Wen, D. Ma, Low-temperature hydrogen production from water and
methanol using Pt/alpha-MoC catalysts, Nature 544 (2017) 80–83.
Ce4+[30]. Comparatively, slightly declined of Ce3+/(Ce3++Ce4+
)
molar ratio from 6.6% and 4.6% after the stability test, which indicated
that CeO2 phase was relatively stable in the reducing atmosphere
during the EATR reaction where CO and H2 generated. Besides, the
Raman result in Fig. S8 also proved the high stability of CeO2 during the
ATR reaction [31]. The variation of the Ce3+/(Ce3++Ce4+) value
15

Z. Xue et al.
CatalysisCommunications108(2018)12–16
[6] S. Luo, L. Zeng, D. Xu, M. Kathe, E. Chung, N. Deshpande, L. Qin, A. Majumder, T.-
L. Hsieh, A. Tong, Z. Sun, L.-S. Fan, Shale gas-to-syngas chemical looping process
for stable shale gas conversion to high purity syngas with a H-2:CO ratio of 2:1,
Energy Environ. Sci. 7 (2014) 4104–4117.
[22] H.-S. Roh, Y. Wang, D. King, Selective production of H2 from ethanol at low tem-
peratures over Rh/ZrO2–CeO2 catalysts, Top. Catal. 49 (2008) 32–37.
[23] A. Trovarelli, Catalytic properties of ceria and CeO2-containing materials, Catal.
Rev. 38 (1996) 439–520.
[7] G.A. Deluga, J.R. Salge, L.D. Schmidt, X.E. Verykios, Renewable hydrogen from
ethanol by autothermal reforming, Science 303 (2004) 993–997.
[8] T. Yamazaki, N. Kikuchi, M. Katoh, T. Hirose, H. Saito, T. Yoshikawa, M. Wada,
Behavior of steam reforming reaction for bio-ethanol over Pt/ZrO2 catalysts, Appl.
Catal. B Environ. 99 (2010) 81–88.
[24] R.R. Davda, J.A. Dumesic, Catalytic reforming of oxygenated hydrocarbons for
hydrogen with low levels of carbon monoxide, Angew. Chem. Int. Ed. 42 (2003)
4068–4071.
[25] X. Han, Y. Yu, H. He, W. Shan, Hydrogen production from oxidative steam re-
forming of ethanol over rhodium catalysts supported on Ce–La solid solution, Int. J.
Hydrog. Energy 38 (2013) 10293–10304.
[26] S.M. de Lima, A.M. da Silva, L.O.O. da Costa, J.M. Assaf, G. Jacobs, B.H. Davis,
L.V. Mattos, F.B. Noronha, Evaluation of the performance of Ni/La2O3 catalyst
prepared from LaNiO3 perovskite-type oxides for the production of hydrogen
through steam reforming and oxidative steam reforming of ethanol, Appl. Catal. A
Gen. 377 (2010) 181–190.
[27] M. Luneau, E. Gianotti, F.C. Meunier, C. Mirodatos, E. Puzenat, Y. Schuurman,
N. Guilhaume, Deactivation mechanism of Ni supported on Mg-Al spinel during
autothermal reforming of model biogas, Appl. Catal. B Environ. 203 (2017)
289–299.
[28] Q. Jin, Y. Shen, S. Zhu, X. Li, M. Hu, Promotional effects of Er incorporation in
CeO2(ZrO2)/TiO2 for selective catalytic reduction of NO by NH3, Chin. J. Catal. 37
(2016) 1521–1529.
[29] F. Liu, L. Zhao, H. Wang, X. Bai, Y. Liu, Study on the preparation of Ni-La-Ce oxide
catalyst for steam reforming of ethanol, Int. J. Hydrog. Energy 39 (2014)
10454–10466.
[30] F. Larachi, J. Pierre, A. Adnot, A. Bernis, Ce 3d XPS study of composite
CexMn1−xO2−y wet oxidation catalysts, Appl. Surf. Sci. 195 (2002) 236–250.
[31] X. Zhang, R. You, D. Li, T. Cao, W. Huang, Reaction sensitivity of ceria morphology
effect on Ni/CeO2 catalysis in propane oxidation reactions, ACS Appl. Mater.
Interfaces 9 (2017) 35897–35907.
[9] D.C. Rennard, J.S. Kruger, L.D. Schmidt, Autothermal catalytic partial oxidation of
glycerol to syngas and to non-equilibrium products, ChemSusChem 2 (2009) 89–98.
[10] M. Compagnoni, A. Tripodi, I. Rossetti, Parametric study and kinetic testing for
ethanol steam reforming, Appl. Catal. B Environ. 203 (2017) 899–909.
[11] S. Crowley, M.J. Castaldi, Mechanistic insights into catalytic ethanol steam re-
forming using isotope-labeled reactants, Angew. Chem. Int. Ed. 55 (2016)
10650–10655.
[12] L. Coronel, J.F. Munera, A.M. Tarditi, M.S. Moreno, L.M. Cornaglia, Hydrogen
production by ethanol steam reforming over Rh nanoparticles supported on lan-
thana/silica systems, Appl. Catal. B Environ. 160 (2014) 254–266.
[13] K. Mudiyanselage, I. Al-Shankiti, A. Foulis, J. Llorca, H. Idriss, Reactions of ethanol
over CeO2 and Ru/CeO2 catalysts, Appl. Catal. B Environ. 197 (2016) 198–205.
[14] C.X. Zhang, S.R. Li, G.W. Wu, Z.Q. Huang, Z.P. Han, T. Wang, J.L. Gong, Steam
reforming of ethanol over skeletal Ni-based catalysts: a temperature programmed
desorption and kinetic study, AICHE J. 60 (2014) 635–644.
[15] A.R. Passos, L. Martins, S.H. Pulcinelli, C.V. Santilli, V. Briois, Effect of the balance
between Co(II) and Co(0) oxidation states on the catalytic activity of cobalt cata-
lysts for ethanol steam reforming, Catal. Today 229 (2014) 88–94.
[16] P. Riani, G. Garbarino, A. Infantes-Molina, E. Rodríguez-Castellón, F. Canepa,
G. Busca, Hydrogen from steam reforming of ethanol over cobalt nanoparticles:
effect of boron impurities, Appl. Catal. A Gen. 518 (2016) 67–77.
[17] A.J. Vizcaino, A. Carriero, J.A. Calles, Hydrogen production by ethanol steam re-
forming over Cu-Ni supported catalysts, Int. J. Hydrog. Energy 32 (2007)
1450–1461.
[18] M.G. Schultz, T. Diehl, G.P. Brasseur, W. Zittel, Air pollution and climate-forcing
impacts of a global hydrogen economy, Science 302 (2003) 624–627.
[19] S. De, J. Zhang, R. Luque, N. Yan, Ni-based bimetallic heterogeneous catalysts for
energy and environmental applications, Energy Environ. Sci. 9 (2016) 3314–3347.
[20] Z. Xue, Y. Shen, S. Zhu, P. Li, Y. Zeng, Z. Xi, Y. Cai, Autothermal reforming of ethyl
acetate for hydrogen production over Ni3La7Oy/Al2O3 catalyst, Energy Convers.
Manag. 146 (2017) 34–42.
[32] K. Rida, M.A. Peña, E. Sastre, A. Martinez-Arias, Effect of calcination temperature
on structural properties and catalytic activity in oxidation reactions of LaNiO3
perovskite prepared by Pechini method, J. Rare Earths 30 (2012) 210–216.
[33] F. Djani, M. Omari, A. Martínez-Arias, Synthesis, characterization and catalytic
properties of La(Ni,Fe)O3–NiO nanocomposites, J. Sol-Gel Sci. Technol. 78 (2016)
1–10.
[34] K. Rida, A. Benabbas, F. Bouremmad, M.A. Peña, A. Martínez-Arias, Surface prop-
erties and catalytic performance of La1−xSrxCrO3 perovskite-type oxides for CO and
C3H6 combustion, Catal. Commun. 7 (2006) 963–968.
́
[35] R.M. Garcıa de la Cruz, H. Falcón, M.A. Peña, J.L.G. Fierro, Role of bulk and surface
[21] H. Chen, H. Yu, F. Peng, G. Yang, H. Wang, J. Yang, Y. Tang, Autothermal reforming
of ethanol for hydrogen production over perovskite LaNiO3, Chem. Eng. J. 160
(2010) 333–339.
structures of La1−xSrxNiO3 perovskite-type oxides in methane combustion, Appl.
Catal. B Environ. 33 (2001) 45–55.
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