Applied Catalysis B: Environmental 286 (2021) 119884

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Applied Catalysis B: Environmental

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

Boosting hydrogen production from steam reforming of ethanol on nickel

by lanthanum doped ceria
Zhourong Xiao a, 1, Chan Wu a, 1, Li Wang a, b, Jisheng Xu a, Qiancheng Zheng a, Lun Pan a, b,
Jijun Zou a, b, Xiangwen Zhang a, b, *, Guozhu Li a, b, *
a
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
b
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China

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

Keywords: Stable and efficient hydrogen production has always been the focus of industry, and steam reforming of ethanol
La doped ceria (SRE) is one of the most robust, renewable and cheap technologies. To develop excellent SRE catalysts highly
Metal-support interaction resisting coke formation and metal sintering, La, Tb, and Zr have been doped as a third metal into Ni-CeO2
Ethanol steam reforming
catalyst using a sol-gel method. The size and dispersion of Ni nanoparticles, surface oxygen vacancies and metal-
Hydrogen production
supported interaction have been finely tuned, with which the catalytic performance is closely associated. La-
doped ceria supported Ni (Ni-CeLa0.20) exhibited superior catalytic performance, which is ascribed to its large
Ni active surface area, abundant oxygen vacancies and suitable metal-supported interaction. DFT calculations
showed that the doping of La into Ni-CeO2 can promote the generation of oxygen vacancies and facilitate the
dissociation of water. On Ni-CeLa0.20, complete conversion of ethanol and stable hydrogen production have been
maintained in the 3000-min test. The coke deposition is only 0.48 mgc/gcat h at 600 ◦ C under the GHSV of 55920
mL/gcat∙h.

1. Introduction
Nowadays most of the energy demands are provided by fossil fuels
which causes serious resource and environmental problems [1–3]. In
this scenario, exploring cheap, sustainable, and environmentally benign
energy sources has captured much attention to replace fossil fuels [3].
Hydrogen is an ideal alternative fuel because it is efficient and clean
with the harmless water as the only by-product. Production of H2 from
steam reforming of renewable oxygenated hydrocarbons, such as
ethanol (Eq. (1)), is a promising technology. Because the feedstock can
be obtained from the fermentation of biomass, avoiding fossil source
problems [4]. However, steam reforming of ethanol is a very complex
process that involves many parallel reactions like dehydration (Eq. (2)),
decomposition (Eq. (3)) and carbon formation reaction (Eqs. (4)–(6)).
C2H5OH + 3H2O → 6H2 + 2CO2
C2H5OH → C2H4 + H2O
C2H5OH → CH4 + CO + H2
2CO → C + CO2 (4)
CH4 → C + 2H2 (5)
C2H4 → Coke (6)
C + H2O→ CO + H2 (7)
To gain insight into the reaction mechanism of SRE and to achieve a
high and stable hydrogen yield, various catalytic systems have been
extensively investigated [2]. Recently, many catalysts based on Pt, Ru,
Co, or Ni were developed for efficient SRE reactions [5–11]. Compared
to the expensive noble metals, the Ni-based catalysts with low cost are
considered as good candidates due to their high activities towards the
rupture of C–C and C–H bonds. However, the main challenges are their
low hydrogen selectivity and bad stability due to serious deposition of
(1)
carbonaceous species and easy sintering of Ni particles [12–17].
(2) Designing new Ni-based catalysts to effectively prevent deactivation
is an urgent issue [18]. Previous studies showed that the synergy of
(3) metal and support is the key to guarantee high activity and stability in

* Corresponding authors at: Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China.
E-mail addresses: zhangxiangwen@tju.edu.cn (X. Zhang), gzli@tju.edu.cn (G. Li).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.apcatb.2021.119884
Received 30 July 2020; Received in revised form 6 December 2020; Accepted 29 December 2020
Available online 11 January 2021
0926-3373/© 2021 Elsevier B.V. All rights reserved.
Z. Xiao et al.
ethanol steam reforming [18–20]. For this reason, the interaction be­
tween metal and support was intensively investigated for an active and
stable SRE process [19,20]. Previous studies showed that Ni-metal
nanoparticles could suppress the formation of filamentous carbon [6,
13]. The Ni nanoparticles were confined by SBA-15 or ordered meso­
porous alumina [6,13,21–23]. Some deactivations were observed on
these catalysts due to coke formation because of the inert support and
weak metal-support interaction. Ceria-based materials received great
attentions as the support of nickel for hydrocarbon reforming owing to
their oxygen storage capacity (OSC) and oxygen mobility (OM) [24–26].
Zhou et al. showed that strong interaction between Ni and ceria in the
Ce1-xNixOy system could effectively turn the electronic structure of
nickel and produce rich active sites, leading to the efficient cleavage of
C–C and C–H bonds during SRE [20]. In addition, the OSC and OM
properties of ceria could further be enhanced by introducing a dopant
[5,7,19,27–29]. Liu et al. showed that Ni and W co-doped ceria
possessed abundant oxygen vacancies that helped partial dissociation of
water [19]. Our group [7] showed that good catalytic performance for
ethanol steam reforming could be achieved by introducing praseodym­
ium (Pr) into ceria.
Previous results spurred us to develop new solid oxides of doped
ceria supported Ni to finely tune the structure of the catalyst and
effectively realize high-performance SRE. Herein, the elements of La, Tb,
and Zr were doped into ceria to prepare new Ni-based catalysts for
hydrogen production by ethanol steam reforming. In order to under­
stand the structure-performance relationship, physicochemical proper­
ties of the catalysts were finely tuned and their catalytic performances
were evaluated. The structures of the catalysts have been well charac­
terized in an attempt to determine the key factors affecting the catalytic
activity and stability for SRE. In addition, DFT + U simulations were
conducted to deeply explore the mechanisms of oxygen vacancy for­
mation and water dissociation on the catalysts.
2. Experimental
2.1. Preparation of the catalysts
In this work, the catalysts were prepared by a sol-gel (SG) method
using citric acid (AR) as the chelating agent [7]. The as-prepared cata­
lysts were named as Ni-CeO2, Ni-La2O3 and Ni-CeLn0.2 (Ln = La, Tb, Zr),
respectively. The Ni loading was fixed to 10 wt% and the mole ratio of
Ce/Ln was 4 for all the catalysts. The metal precursors were Ni
(NO3)2∙6H2O, La(NO3)3∙6H2O, Ce(NO3)3∙6H2O, Zr(NO3)4∙2H2O, Tb
(NO3)3∙6H2O with AR purity, which were purchased from Beijing
HWRK Chem Co. The detailed procedure for the synthesis of Ni-CeLn0.2
is as follows: the metal precursors of Ni(NO3)2∙6H2O, Ce(NO3)3∙6H2O
and Ln(NO3)3∙xH2O were simultaneously added in a 500 ml beaker, and
then citric acid solution was introduced. The amount of citric acid is
twice that of metal ions. In particular, for the synthesis of Ni-CeLa0.2,
5.453 g of Ce(NO3)3∙6H2O, 1.359 g of La(NO3)3∙6H2O and 1.486 g of Ni
(NO3)2∙6H2O were mixed with citric acid solution (20 mL). The amount
of citric acid in the solution was 7.991 g. The resulting solution was
stirred for 12 h at 60 ◦ C, and then heated to evaporate water and then
dried at 120 ◦ C to form spongy solid. The solid was grinded, placed in a
quartz boat and calcined at 600 ◦ C in air for 4 h. In addition, a control
catalyst of CeLa0.2 supported Ni was synthesized using the traditional
impregnation (IMP) method, which is similar to those reported previ­
ously [1,11], and the catalysts were denoted as Ni-CeLa0.2-IMP. Firstly,
CeLa0.2 was synthesized using a similar procedure of Ni-CeLa0.2 prepa­
ration. Then, a solution of Ni(NO3)2∙6H2O (2.04 mol/L, 2.5 mL) was
added in 2.700 g of the as-prepared CeLa0.2. The mixture was kept 12 h
at room temperature. The obtained solid was dried at 120 ◦ C for 24 h and
calcined at 600 ◦ C for 4 h. In order to characterize the structure of the
reduced catalyst, in-situ reduction by H2 at 500 ◦ C for 1 h was carried
out.
2
Applied Catalysis B: Environmental 286 (2021) 119884
2.2. Characterization
XRD were tested on Rigaku D8-Focus diffractometer equipped with
Cu Kα radiation (λ =1.54056 Å) at the 2θ values range of 20◦ - 85◦ with a
scan rate of 8◦ /min. The N2 adsorption-desorption was collected on
Micromeritics Tristar 3000 analyzer at -196 ◦ C. 0.12 g of the sample was
first heated at 300 ◦ C under vacuum for 4 h. The specific surface area of
the sample was calculated by BET method, and pore volume and average
pore diameters were obtained from BJH method using desorption data.
H2-TPR and O2-TPO measurements were performed on an AMI-300 in­
strument. In a H2-TPR typical test, 0.1 g of the sample was first degassed
at 400 ◦ C for 1 h, then cooled to 50 ◦ C, and finally a H2-Ar (10 vol%, 30
mL/min) was introduced. Then the sample was raised to 800 ◦ C at a
heating rate of 10 ◦ C/min. For the test of O2-TPO, 0.03 g of the spent
catalyst was degassed at 150 ◦ C under Ar atmosphere, then a O2-Ar (5
vol%, 30 mL/min) was introduced after cooled to 50 ◦ C. Then the
sample was heated to 800 ◦ C at a rate of 10 ◦ C/min. H2 chemisorption
(H2-TPD) was recorded in an Autochem 2920 (Micromeritics). The as-
prepared sample was reduced with H2/Ar (10 vol%, 30 mL/min) at
500 ◦ C for 1 h, then cooled to 50 ◦ C under Ar flow. H2 was introduced to
the as-reduced catalysts until H2 saturation. Then, the temperature was
raised to 800 ◦ C at a rate of 10 ◦ C/min. According to the amount of
chemisorbed H2, the Ni dispersion was calculated, in which we assumed
that one surface Ni atom adsorbed one hydrogen atom. EPR was con­
ducted on Bruker E500 spectrometer at -196 ◦ C. ICP-OES was measured
on an Optima 5300DV (Perkin Elmer). UV–vis DRS were collected on a
Hitachi U-3010 spectrometer. Raman spectra were recorded on a DXR
Microscope system with 532 nm as laser source. SEM images were
collected on FEI Nanosem 430. The TEM images of the catalysts were
collected on a JEM-2100 F microscope under a working voltage of 200
kV. TG was recorded on TQ-500. The experiments of TG were performed
in air flow (50 mL/min) from room temperature to 800 ◦ C at a heating
rate of 10 ◦ C/min. The coke deposition rate was calculated based on the
data of TG and the reaction time. The coke amount in the spent catalyst
was calculated using the mass loss percentage from the TG data. In order
to eliminate the effect of mass increase by nickel oxidation, the data that
after complete oxidization of Ni species were used. Then, coke deposi­
tion rate was calculated via dividing the coke amount by the reaction
time. The XPS were measured on an ESCALAB 250Xi spectrometer with
Al Kα radiation (hν = 1486.6 eV). The binding energy of the C 1s peak
from adventitious carbon was set at 284.8 eV to correct the charge
effects.
2.3. Catalyst evaluation
The catalytic steam reforming of ethanol was carried out in a stain­
less steel fixed-bed tubular reactor (6 mm ID) at atmospheric pressure
loaded with a mixture of 0.25 g catalyst (20–40 mesh) and 1.2 g silicon
carbide (20–40 mesh). Prior to the reaction, the catalyst was activated
by H2 for 1 h at 500 ◦ C. Then N2 (60 mL/min) was used as a carrier gas
and purged the pipeline. The ethanol solution (0.255 mL/min) was
introduced to the reactor by high performance liquid chromatography
pump. The molar ratio of water to ethanol was fixed to 4 and gas hourly
space velocity (GHSV) of ethanol solution was set to 55920 mL/gcat∙h.
The mixed liquid was heated and evaporated at 300 ◦ C in an evaporator
before entering the catalytic bed. A gas chromatograph (Varian Micro-
GC 490), which was equipped with three columns of activated
alumina, PPU and 5 Å molecular sieve and with the detectors of TCD,
was used to analyze the gas products online. Activated alumina column
was used for detecting light hydrocarbons such as ethane and ethylene.
The PPU column was adopted to analyze CO2. The 5 Å molecular sieve
column was employed for the analyses of H2, N2, CH4, CO. The con­
version of ethanol and gas product rate were calculated using Eqs. (8)–
(9) [29].
Z. Xiao et al. Applied Catalysis B: Environmental 286 (2021) 119884

Fout out out

CO + FCO2 + FCH4
Ethanol conversion (wt%) = in
× 100 (8) ∆E = EH∗+OH∗ − EH2 O∗ (12)
Fethanol
EH2 O∗ and EH∗+OH∗ represent the energies of optimized initial and final
/
AH2 ⋅fH2 states for water dissociation, respectively.
Gas product rate (μmol min) R(H2 ) = × R(N2 ) (9)
AN2 ⋅fN2

Fethonal + Fgas 2.5. Description of the relationship between structure and activity
Carbon balance (wt%) = cout cout
× 100 (10)
Fethanol
cin
The relative oxygen vacancy concentration was calculated based on
where AH2 represents GC peak area of hydrogen, fH2 represents the the intensity of EPR peak. The peak intensity of Ni-CeO2 possessing the
response factor of hydrogen, and RN2 is the nitrogen flow rate (60 mL/ lowest oxygen vacancy concentration was set as the standard and
min). defined as 1. Exceptionally, the relative oxygen vacancy concentration
of Ni-CeLa0.2-IMP was calculated based on Raman spectra. The relative
metal-support interaction was calculated based on the reduction peak
temperature. Ni-CeLa0.2-IMP possessing the lowest reduction peak
2.4. DFT simulation
temperature was set as 1. The relative activity was calculated based on
the reaction data in Fig. 6a. The ethanol conversion on Ni-CeLa0.2-IMP
In terms of electronic structure of pure ceria and metal doped ceria,
was defined as 1 due to its lowest value at 550 ◦ C.
DFT + U method was performed. According to previous studies, the U
values for Ce is 4.5 eV [30–35].
The ceria surface was modeled by (3 × 3) unit cells as a nine atomic 3. Results and discussion
layer (three O-Ce-O tri-layers) slab with 15 Å vacuum space. The energy
cutoff of 450 eV was adopted, and the Monkhorst Pack scheme was 3.1. Characterization of the as-prepared fresh catalysts
sampled with (2 × 2 × 1) k-point. Structure optimization were allowed
to relax until the forces of all atoms were less than 0.02 eV/Å. Fig. 1 displays the XRD patterns of the reduced catalyst. The fluorite
Formation energy of the oxygen vacancy (Evac structure of ceria could be clearly observed in all the samples including
f ) is formulated and
pure ceria, La doped ceria and the catalysts of metal (La, Tb, or Zr) doped
defined as Eq. (11) which could be seen [7].
ceria supported Ni [7]. As shown in Fig. 1a, the peaks corresponding to
Efvac = E(CeO2− x ) + 1 2 E(O2 ) − E(CeO2 )
/
(11) La2O3, TbO2, and ZrO2 did not appear in the as-prepared catalysts,
indicating the formation of solid solution. Fig. 1b displays the XRD
The dissociation energy of water (∆E) was defined by Eq. (12) [36,37]. patterns of La2O3 supported Ni (Ni-La2O3) and La doped ceria supported

Fig. 1. (a–b) Wide-angle XRD patterns of the reduced catalysts. The peaks labeled by ▴, ◆, ♣ and Δ are the characteristic peaks of CeO2, Ni, La2O3 and LaNiO3,
respectively. (c) The enlarged XRD patterns in the 2θ range of 43˚-46˚. (d) The enlarged XRD patterns in the 2θ range of 27˚-30˚.

3
Z. Xiao et al.
Ni prepared by the IMP method (Ni-CeLa0.2-IMP). For the sample of
Ni-La2O3, the crystalline of La2O3 as well as some LaNiO3 was detected,
which corresponds to the perovskite phase with rhombohedral structure
(JCPDF-330711) [27]. Meanwhile, the absence of Ni peak at 44.5◦
suggests (Fig. 1c) that Ni nanoparticles were amorphous or the particle
size was too small to be detected [29]. Because all the catalysts were
prepared by H2 reduction at high temperature, amorphous Ni nano­
particles hardly existed. Therefore, it can be deduced that small Ni
nanoparticles were highly dispersed on corresponding support for the Ln
(La, Tb, Zr)-doped catalysts prepared by the SG method. In comparison,
the Ni peak at 44.4◦ is strong for Ni-CeLa0.2-IMP as shown in the Fig. 1b
and c. It indicates the presence of large Ni particles in Ni-CeLa0.2-IMP.
The results illustrate that the SG method is superior to the IMP method in
decreasing Ni particle size and improving their dispersion on the sup­
port. Moreover, we speculate that Ni particles and the support (CeO2,
metal doped CeO2, or La2O3) strongly interacted in the catalyst prepared
by the SG method. The aggregation of Ni nanoparticles during
high-temperature reduction will be effectively suppressed by the strong
metal-support interaction.
Compared with the peak 2θ value of pure CeO2, corresponding
diffraction 2θ value of La doped ceria shifted to lower angle. It is
attributed to the fact that the radius of La3+ (1.10 Å) is larger than that of
Ce4+ (0.97 Å), which leaded to the crystal lattice expansion [5]. The
peaks of La doped ceria were weaker and broader than those of pure
ceria, which indicates that La species were homogeneously doped into
ceria lattice. The same trend was observed for Ni-CeO2 and Ni-CeLa0.2. It
is expected that the anti-sintering ability of the catalyst is improved by
the lattice doping of lanthanum. In comparison, the sample of Zr doped
ceria supported Ni showed that its diffraction peaks slightly shifted to
higher angle. Similarly, it is ascribed to the smaller radius of Zr4+ (0.84
Å) than that of Ce4+ (0.97 Å), leading to the contraction of the crystal
lattice. The diffraction peaks of Tb doped ceria supported Ni also slightly
shifted to lower angle. The ionic radius of Tb3+ is 1.04 Å, while that of
Tb4+ is 0.88 Å [38]. Therefore, both valance states of Tb were present in
the sample, and Tb3+ was dominant to lead lattice expansion. All the cell
lattice parameters were calculated and presented in Table 1. The
changes of cell lattice parameter show that La or Tb doping expanded
the crystal lattice of ceria, while Zr doping caused lattice contraction.
Table 1 summarizes the textural properties of the samples. All the
samples show the type IV isotherm with the characteristic hysteresis
loop (Fig. S1), suggesting the presence of mesoporous structure. Their
BET surface areas range from 18 m2/g to 30 m2/g.
SEM images of Ni-CeLa0.2 are presented in Fig. S2. The EDX results
show that the elements of O, La, Ce and Ni were all present (Figs. S2b,
2c, 2d and 2e). The elements were uniformly distributed, which
benefited from the SG method. As shown in Fig. S2g, the amount of Ni
was 10.11 wt% and the mole ratio of Ce/La was 3.7, which are consis­
tent with the theoretical values. Similar results were obtained for Ni-
CeO2, Ni-CeZr0.2 and Ni-CeTb0.2 (Figs. S2, S3, S4 and S5), demonstrating
that Ni nanoparticle were highly dispersed in the Ce-Ln (La, Tb and Zr)
solid oxides, which well matched with the XRD results.
HAADF images of Ni-CeLa0.2 are shown in Fig. 2a, and corresponding
Table 1
Textural properties of the samples.
Catalysts BET Surface Pore Volume Average Pore Cell lattice
Area (m2/g) (cm3/g) Size (nm) Parameter (Å)a
Ni-CeO2 29.37 0.056 3.98 5.412
Ni-CeLa0.2 20.71 0.042 8.71 5.442
Ni-La2O3 23.30 0.041 8.76 –
Ni-CeLa0.2- 16.63 0.076 16.44 5.440
IMP
Ni-CeTb0.2 16.06 0.052 9.81 5.423
Ni-CeZr0.2 18.23 0.048 8.62 5.395
a
The cell lattice parameter was calculated by (111) facets of ceria using the
Scherrer equation.
4
Applied Catalysis B: Environmental 286 (2021) 119884
elemental distributions of O, Ce, La and Ni are presented in Fig. 2b–e.
The elements of O, Ce and La were uniformly distributed, which in good
agreement with the SEM images (Fig. S2). The uniformly loaded small Ni
metal particles possessed enhanced interfacial contacting with the
CeLa0.2 support. For Ni-CeLa0.2-IMP, the elements of O, Ce and La were
also uniformly distributed, which benefited from the preparation of the
CeLa0.2 support by the SG method. However, the Ni metal species in Ni-
CeLa0.2-IMP exhibit some agglomeration and uneven distribution, which
is consistent with our XRD results (Fig. 1c) and the previous reports [1,
11]. This may be caused by weak interaction between Ni metal and the
support, which will be further discussed in latter section based on the
TPR analysis.
ICP was employed to accurately quantify the nickel amount in the
catalyst (Table 2). All the catalysts loaded reasonable amount of nickel
metal, which was very close to the theoretical value of 10 wt %. The
amount of dopant was also similar to the theoretical value, which
matches well with the SEM-EDX analysis.
The reduction behaviors of the as-prepared catalysts were studied by
H2-TPR, and the results are presented in Fig. 3. For the freestanding NiO,
a small reduction peak at 317.8 ◦ C was detected followed by a sharp
peak at 382.6 ◦ C due to the big particle size. Two reduction peaks rep­
resented the reduction behavior of NiO undergoing the reaction of
NiO→Niσ+→Ni◦ [39]. For the Ni catalysts supported by ceria or metal
(La, Tb, Zr) doped ceria, three reduction peaks (α, β, γ) were presented.
The first peak (α) located at low reduction temperature is responsible for
surface adsorbed oxygen species, which is easily to be reduced under H2
atmosphere [40]. The second peak (β) was ascribed to the reduction of
bulk NiO that weakly interacts with the support. The third peak (γ) was
attributable to the reduction of relative small NiO particles strongly
interacting with ceria [7,39]. Compared with the peaks of Ni-CeO2, the
reduction peaks of β and γ shifted to higher temperature for Ni-CeLa0.2
and Ni-CeZr0.2. It illustrates the enhanced metal-support interaction by
the doping of La or Zr into ceria. When Tb doped ceria was used as the
support, the peaks of β and γ moved to lower reduction temperature. The
areas of γ peak were all increased by the introduction of La, Tb, and Zr
into ceria using the SG method. For Ni-CeLa0.2-IMP prepared by the
impregnation method, the main reduction peak was the β peak. It il­
lustrates the nickel oxides species were mainly large NiO particles which
possessed relative weak metal-supported interaction. These results are
in accord with the XRD (Fig. 1) and TEM (Fig. 2) data. For Ni-La2O3, the
first peak (I) appeared at 416.9 ◦ C and can be ascribed to the reduction
of surface Ni2+ species. The second peak (II) appeared at temperature of
609.3 ◦ C, indicating the reduction of LaNiO3 to La2Ni2O5. The third peak
(III) at 767.7 ◦ C corresponded to the reduction of Ni2+ in LaNiO3 to
metallic Ni [41]. According to the XRD results (Fig. 1), the LaNiO3
perovskite was formed which needs high reduction temperature.
H2-TPD was measured to determine Ni dispersion and active Ni
surface area. The data are shown in Table 2. Both the active Ni surface
area and the Ni dispersion were improved by the introduction of La, Tb,
or Zr into ceria. It is ascribed to their high proportion of Ni species that
strong interact with the support. The catalyst of Ni-CeLa0.2 possessed the
highest Ni active surface area (26.5 m2/g) and Ni dispersion (17.7 %). In
comparison, Ni-CeLa0.2-IMP showed the active Ni surface area of only
8.4 m2/g and the Ni dispersion of 5.6 %, which are less than one third of
Ni-CeLa0.2. Therefore, the SG method can effectively improve the
dispersion of Ni and increase Ni active surface area [5], as demonstrated
by XRD (Fig. 1), TEM (Fig. 2) and TPR (Fig. 3). Previous study showed
that the dispersion and anti-sintering performance of Ni particles could
be effectively promoted by their strong and intimate interacts with the
support [19]. Moreover, the Ni particles in close contact with ceria could
guarantee the sufficient supply of OH from the surrounding ceria, which
can enhance carbon gasification [20]. Therefore, it is expected that the
highly dispersed Ni particles supported on metal doped ceria show good
performance for SRE.
The nature of catalyst support directly influences the catalytic per­
formance in the SRE process. For the redox supports of ceria and metal-
Z. Xiao et al. Applied Catalysis B: Environmental 286 (2021) 119884

Fig. 2. a) HAADF image of Ni-CeLa0.2, b-e) corresponding elemental distributions of O, Ce, La, and Ni, and f) the overlapping of Ce, La, Ni elements. g) HAADF of Ni-
CeLa0.2-IMP, h-k) corresponding elemental distributions of O, Ce, La, Ni, and l) the overlapping of Ce, La, Ni elements.

doped ceria, their oxygen vacancies help to dissociate water and form
surface hydroxyl groups [20,42]. In order to gain insight into the oxygen
vacancies and oxygen storage-release capability (OSC) in the catalysts,
Raman spectroscopy was adopt due to its high sensitivity to Ce-O bond
vibration and lattice defects [28]. For pure ceria (Figure S6), the sharp
peak at 465 cm− 1 is ascribed to the fluorite structure vibration (F2g
mode). After metal doping (La, Tb, or Zr) (Figs. S6 and 4 a), the shift of
the F2g peak suggests the formation of homogeneous solid oxide, which
is also confirmed by the XRD data (Fig. 1). The weak peaks of F2g mode
for the Tb and Zr doped samples are ascribed to their stronger fluores­
cence effects which reduced the detectable of Raman signal [43]. No
Raman response was observed for Ni-La2O3, which is ascribed to the non

5
Z. Xiao et al. Applied Catalysis B: Environmental 286 (2021) 119884

Table 2
Bulk phase composition, Ni dispersion and active Ni surface area of the reduced catalysts.
Catalysts Ni (wt%)a Ce (wt%)a La (wt%)a Tb (wt%)a Zr (wt%)a Ni dispersion (%)b Ni active surface areas (m2/gNi)c

Ni-CeO2 9.92 90.08 – – – 12.5 18.7

Ni-CeLa2 9.99 71.95 18.06 – – 17.7 26.5
Ni-La2O3 9.96 – 90.04 – – 16.3 24.4
Ni-CeLa2-IMP 9.97 71.86 18.17 – – 5.6 8.4
Ni-CeTb2 9.98 71.46 – 18.56 – 16.9 25.3
Ni-CeZr2 9.94 72.03 – – 17.03 15.2 22.7
a
Calculated based on ICP results.
b
The dispersion of Ni was estimated by the data of H2-chemisorption, which was equal to the ratio of Ni atoms on the surface and total Ni atoms.
c Ni atoms on the surface SNi ∗ M 2
D= = p . Where SNi is the represents the Ni metal surface area (m /gNi), N is Avogadro’s number, A is the metal surface area per
Total Ni atoms N∗A∗
100
atom (for Ni, A = 6.494*10− 20 m2/atom).

Fig. 3. TPR profiles of the as-prepared catalysts.

cubic fluorite-type crystal structure. Besides the F2g mode, two other
Raman peaks located at 550 cm− 1 and 610 cm− 1 were detected, which
can be differentiated from that of NiO (513 cm− 1). The two peaks are
assigned to oxygen vacancies in the lattice [7,44]. Both Raman modes
come from the substitution of Ce4+ by other dopant (La, Zr, Tb or Ni) or
the lattice changes originating from the ionic radii disparity between
Ce4+ and the dopant (La, Zr, Tb or Ni) [1,7,43]. Compared with pure
ceria, the relative content of oxygen vacancies was sharply incerased
after the doping by La, Zr, Tb or Ni.
UV–vis diffuse reflectance spectroscopy was used to illustrate the
electronic state of the metal ions, and the data are shown in Fig. S7. Two
peaks located at 233 nm and 270 nm could be obviously observed, which
can be assigned to O2− →Ce3+ and O2− →Ce4+ charge-transfer transi­
tions, respectively [44,45]. Compared with Ni-CeO2, the metal (La, Tb,
Zr) doped Ni-CeO2 exhibited higher peak intensities of the (O2− →Ce4+)
and (O2− →Ce3+) bands, which is explained by the increasing number of
oxygen vacancies [45]. The peak intensities for (O2− →Ce4+) and
(O2− →Ce3+) bands in Ni-CeLa0.2-IMP was low, indicating that many Ni
atoms were not inserted into ceria lattice.
To further characterize the oxygen vacancies, the measurements of
EPR and XPS were conducted. As shown in Fig. 4b, Ni-CeO2 and metal
(La, Tb, Zr) doped Ni-CeO2 showed symmetrical EPR signals (g = 1.996)
due to the existence of oxygen vacancies [37]. Obviously, compared the
un-doped sample (Ni-CeO2), metal (La, Tb, Zr) doped samples possessed
stronger EPR signals. The doping of La, Tb, or Zr into ceria could
effectively increase the concentration of oxygen vacnacies. The
increased EPR singal by Zr doping is attributed to the contraction of the
crystal lattice due to the different ionic radii of Ce and Zr. Because Zr4+
and Ce4+ have the same valence state. The enhanced oxygen vacancy
concentation by Tb doping is ascribed to the existing of two valence
states of Tb (Tb4+, Tb3+), which caused more complex crytal lattice
changes. When Ce4+ was substituted by aliovalent ions (Tb3+), more
oxygen vacancies were generated to ensure the charge neutrality in the
ceria lattice [44]. In particular, the highly intensive signal of Ni-CeLa0.2
suggest the presence of abundant oxygen vacancies. It is explained by
the large crystal lattice expansion caused by the extensive substitution of
Ce4+ by aliovalent ions (La3+) with different ionic radius and valence.
The XPS spectra of O-1 s and Ce-3d are shown in Figs. 4c and S8a.
The shifting of O-1 s and Ce-3d peaks to lower binding energy demon­
strates the formation of some oxygen defects on the surface [37]. In the
O-1 s core level region (Fig. S8c), the sharp peak centered at 529 ± 0.5
eV (OI) is attributed to the lattice oxygen, and the peak at 531 ± 1 eV
(OII) is associated with chemisorbed oxygen species (Oα) and hydroxyl
species (Oβ) on the surface [40]. The OII peak was observed in most
synthesized materials, and generally regarded as the presence of oxygen
vacancies. With the doping of La, Tb, or Zr, the peak intensity of OII was
increased, indicating the existence of abundant oxygen vacancies. The
relative concentration of oxygen vacancies is as follows: Ni-CeLa0.2 >
Ni-CeTb0.2 > Ni-CeZr0.2 > Ni-CeO2. These results match well with the
EPR analysis. Moreover, similar results could be obtained in terms of O-1
s and Ce-3d XPS spectra for the catalysts treated in hydrogen at 500 ◦ C
for 1 h (Figs. S8c and S8d). Compared with Ni-CeO2, Ni-CeLa0.2 doped
with La possessed increased contents of both oxygen vacancies and Ce3+.
The concentration of Ce3+ was calculated based on the results of XPS
curve fitting (Fig. S8d) following the assignment reported by Trudeau
et al. [46]. Specifically, the ratio of Ce3+/(Ce3++Ce4+) was increased to
0.23 in Ni-CeLa0.2 compared with that in Ni-CeO2 (0.16).
In order to know more about the information of oxygen vacancies,
DFT + U method was adopted to simulate the redox behaviors of various
ceria surfaces (bare CeO2, La-doped CeO2, Ni-doped CeO2 and Ni-La-co-
doped CeO2) [33,47]. Previous studies showed that surface oxygen va­
cancy can help to dissociate water and oxidize carbon [34,48]. With this

6
Z. Xiao et al.
Fig. 4. a) Raman profiles, b) EPR spectra, and c) O 1s XPS spectra of the as-prepared catalysts before H2 treatment.
consideration, oxygen vacancies are demanded on the ceria supported
Ni catalyst to enhance catalytic performance for ethanol steam reform­
ing [49]. After the optimization of different ceria (111) surfaces, the
formation energies of oxygen vacancies were calculated, and the results
are summarized in Fig. S9. CeO2(111) possessed higher formation en­
ergy of oxygen vacancy than La-CeO2(111) and Ni-CeO2(111). The
formation energy of oxygen vacancies on Ni-La-CeO2(111) is only − 0.96
eV, which is much lower than that of Ni-CeO2(111) (− 0.24 eV). It in­
dicates that La doping can promote the generation of oxygen vacancies.
Thus, the conclusions drawn based on the experimental data of Raman
(Fig. 4a), EPR (Fig. 4b) and XPS (Figs. 4c, d and S8c, d) can be properly
explained.
Moreover, the dissociation energies of water on CeO2(111), Ni-doped
CeO2(111) and Ni-La-co-doped CeO2(111) surface were calculated, and
the results are plotted in Fig. 5. The dissociation of H2O to OH and H on
Ni doped CeO2(111) and Ni-La co-doped CeO2(111) is easy to occur. As
shown in Fig. 5, the relative dissociation energies (ΔE) of water on
CeO2(111), Ni-CeO2(111) and Ni-La co-doped CeO2(111) surface are
-0.01 eV, -0.21 eV, and -0.25 eV, respectively. Therefore, the presence of
doped Ni and La in ceria plays a crucial role in dissociating water and
generating abundant surface hydroxyl groups [19], which will be
beneficial to SRE reaction.
3.2. Catalytic activity and stability of the catalysts
In order to figure out the effect of dopant on catalytic performance,
the initial catalytic activities of all the catalysts for SRE were evaluated.
The reaction temperature was set in the range of 500–650 ◦ C, and the
experimental data are shown in Fig. 6a and Table S1. At low reaction
temperature, relative low ethanol conversion and hydrogen production
rate (HPR) were observed on the catalysts prepared by the SG method.
C2 was detected in the product, indicating the weak activity of Ni for
7
Applied Catalysis B: Environmental 286 (2021) 119884
breaking C-C at low temperature. With the increase of reaction tem­
perature, both ethanol conversion and hydrogen formation rate were
remarkably increased, which is ascribed to the endothermic property of
SRE reaction. The catalysts prepared by the SG method exhibited higher
activity and HPR than that synthesized by the IMP method. Moreover,
the ethanol conversion and HPR were further improved by the doping of
La, Tb, or Zr into the catalyst. Ni-CeLa0.2, Ni-CeTb0.2, and Ni-CeZr0.2
exhibited superior performance in comparison to Ni-CeO2 without any
metal doping. In particular, the conversion of ethanol at the temperature
of 550 ◦ C is in the order of Ni-CeLa0.2 (87.6 %) > Ni-CeTb0.2 (82.9 %) >
Ni-La2O3 (80.7 %) > Ni-CeZr0.2 (75.4 %) > Ni-CeO2 (72.7 %) > Ni-
CeLa0.2-IMP (63.9 %). Similar trend was obtained for the generation rate
of H2 (Table S1). The temperatures for complete conversion of ethanol
catalyzed by metal (La, Tb, Zr) doped ceria supported Ni are all lower
than that over Ni-CeO2 as shown in Fig. 6a.
The catalytic activities are related with the concentration of oxygen
vacancies and the state of metal-support interaction as shown in Fig. 6b.
As determined by Raman (Fig. 4a), EPR (Fig. 4b), XPS (Fig. 4c), DFT
calculations (Figs. 5 and S9) and TPR (Fig. 3), Ni-CeLa0.20 and Ni-
CeZr0.20 possessed the high Ce3+ ratio, abundant oxygen vacancies as
well as enhanced metal-support interaction compared with Ni-CeO2.
Although the metal-support interaction in Ni-CeTb0.2 was weaker than
that in Ni-CeO2, its higher concentration of oxygen vacancies and rela­
tive larger active Ni surface area endowed Ni-CeTb0.2 with high per­
formance for ethanol conversion and hydrogen production (Fig. 6b).
Though abundant oxygen vacancies existed in Ni-La2O3 (Fig. S8c), its
excessively strong metal-support interaction (Fig. 3) caused that most of
the Ni active sites could not to be utilized. In fact, the oxygen storage
release capability and oxygen mobility of La2O3 are weaker than those of
ceria as reported by Cristina et al., [1]. Thus, Ni-La2O3 may exhibit
relatively high initial activity but bad long-time stability. This deduction
will be confirmed by the stability test in latter section (Fig. 7).
Z. Xiao et al. Applied Catalysis B: Environmental 286 (2021) 119884

Fig. 5. The relative dissociation energies of H2O (△E) on CeO2 (111), Ni-CeO2 (111) and Ni-La co-doped CeO2 (111) surface.

Fig. 6. a) Conversion of ethanol under different reaction temperatures over different catalysts. Reaction conditions: H2O/C = 2, GHSV of C2H5OH solution = 55920
mL/gcat⋅h, P =1 atm, N2 = 60 mL/min. b) The relationship of relative catalytic activity, oxygen vacancy concentration and metal-support interaction.

8
Z. Xiao et al.
Fig. 7. The conversion of ethanol and hydrogen production rate with time on stream over (a) Ni-CeO2, (b) Ni-La2O3, (c) Ni-CeLa0.2-IMP, (d) Ni-CeLa0.2, (e) Ni-
CeTb0.2 and (f) Ni-CeZr0.2 at the GHSV of 55920 mL/gcat⋅h for C2H5OH solution, reaction conditions: T =600 ◦ C, H2O/C2H5OH = 4, P =1 atm, N2 = 60 mL/min.
The stability test was carried out at 600 ◦ C and atmospheric pressure
under H2O/C2H5OH ratio of 4 and ethanol solution GHSV of 55920 mL/
gcat∙h. As shown in Figs. 7 and S10, catalysts prepared by the SG method
possessed higher activity and stability than that synthesized via the IMP
method (Ni-CeLa0.2-IMP). For Ni-CeLa0.2-IMP, the conversion of ethanol
declined quickly from 76.6 % to only 40.7 % after 120 min (Fig. 7c).
Similarly, HPR was decreased from 5677.2 μmol/min to 2900.7 μmol/
min finally. The rapid deactivation of Ni-CeLa0.20-IMP in SRE may be
explained by the serious metal-sintering and severe coking on the
catalyst. On Ni-La2O3 (Fig. 7b), the conversion of ethanol was decreased
from 99.2% to 60.5% in the first 300 min, and then gradually declined to
57.4 %. The HPR was decreased from 6692.3 μmol/min to 3925.7 μmol/
min after 1500 min. As catalyzed by Ni-CeO2, the conversion of ethanol
was reduced gradually from 88.8% to 70.1% with the HPR dropped from
6245.9 μmol/min to 5179.9 μmol/min in 3000 min. With the intro­
ducing of dopants (Ni-CeLa0.2, Ni-CeTb0.2, Ni-CeZr0.2), both the con­
version of ethanol and HPR were increased. For Ni-CeZr0.2, the slightly
decreased ethanol conversion from initial 95.8 % to final 72.5 % was
9
Applied Catalysis B: Environmental 286 (2021) 119884
caused by some coking, which can be attributed to its relative small
amount of oxygen vacancies (Fig. 4b). Oxygen vacancies are necessary
to maintain stable reaction. On Ni-CeTb0.2, ethanol conversion was
decreased from 100 % initially to 83.6 % finally. The decreased catalytic
performance may be ascribed to the sintering of Ni due to its relative
weak metal-support interaction (Fig. 3). In particular, on the La doped
catalyst (Ni-CeLa0.2), complete conversion of ethanol without any active
loss has been achieved throughout (3000 min) and the HPR was still as
high as 8057.3 μmol/min in the final. The highly enhanced ethanol
steam reforming performance was attributed to the effectively sup­
pressed coke deposition by the highly dispersed Ni nanoparticles (Fig. 2
and Table 2) with suitable metal-support interaction and rich oxygen
vacancies. Previously, Ma et al. [6] pointed out that the catalytic activity
can be closely related to Ni active surface area. Cristina et al. [1] showed
that carbonaceous species could be easily oxidized by the oxygen va­
cancies on catalyst surface. Moreover, our catalysts were tested in higher
ethanol solution GHSV of 93200 mL/gcat∙h, and the data are displayed
in Figs. S11 and S12. The La doped sample (Ni-CeLa0.2) showed much
Z. Xiao et al.
higher ethanol conversion, larger hydrogen production rate as well as
better stability compared with Ni-CeO2. These results further prove that
La doping into ceria could enhance the catalytic performance of sup­
ported Ni catalyst which benefit from highly dispersed of Ni and rich
oxygen vacancies.
As reported in previous studies, many novel Ni or promoted Ni-based
catalysts with various structures were developed and used in SRE under
different reaction conditions. As summarized in Table S2, the Ni
component, water to carbon ratio, reaction temperature, initial activity,
activity loss percentage and carbon deposition are presented and
compared with those of the La doped ceria supported Ni (Ni-CeLa0.2)
developed in this work. Relatively higher activity, better stability and
less carbon deposition were achieved on Ni-CeLa0.2, which is a
competitive candidate for efficient industrial SRE.
3.3. Characterization of the spent catalysts
To reveal the key factors affecting catalytic performance, the struc­
tures of the spent catalysts were characterized by various technologies.
As shown in Fig. 8, any peak that can be assigned to Ni species was not
observed on the spent metal-doped catalysts (Ni-CeLn0.2) and Ni-La2O3.
It illustrates that the high dispersion of Ni nanoparticles were main­
tained under the harsh reaction conditions for long time. For the used
catalyst of Ni-CeO2, the diffraction peaks of both Ni and CeO2 were
observed with high intensity, which indicates the sintering of metal Ni
species and ceria support to some extent. These results demonstrate that
the metal doping into ceria could effectively improve the stability of the
catalysts by tuning metal-support interaction [50]. In the TPR profiles,
the reduction temperature for Ni-CeTb0.2 was lower than that of Ni-CeO2
(Fig. 3b), resulting in its higher catalytic performance for SRE. For the
catalyst prepared by the IMP method (Ni-CeLa0.2-IMP), La doping could
greatly increase the concentration of oxygen vacancies (Fig. 4a), but its
weak metal-support interaction leaded to serious sintering of Ni species.
The diffraction peak of Ni species with high intensity could be obviously
observed for the spent Ni-CeLa0.2-IMP. In addition, new diffraction peak
located at 26.4◦ was detected which is assigned to graphitic carbon [29].
Previous studies reported that the growth of nickel particles by Ostwald
ripening was one of the major reasons for catalytic deactivation [40]. In
this work, the sharply decreased catalytic performance of Ni-Ce­
La0.2-IMP for SRE is attributed to the serious sintering of Ni species.
Apart from the sintering of Ni species, coking is another important
factor causing the deactivation of the catalyst. Coke deposition was
characterized by TEM for all the spent catalysts (Fig. S13). On the spent
Ni-CeO2, both filamentous carbon and amorphous carbon were
observed. In some case, filamentous carbon with Ni particle on its tip
was generated. These Ni species could still provide some active sites for
Fig. 8. XRD patterns of the spent catalysts. The main peaks of CeO2, Ni, La2O3,
LaNiO3 and carbon are labeled by ♠, ◆, ♣, Δ respectively.
10
Applied Catalysis B: Environmental 286 (2021) 119884
SRE [7]. In addition, some large Ni particles with the size of up to 20 nm
were detected, which verifies the sintering of nickel under the reaction
condition. On the spent Ni-CeLa0.2-IMP, many large Ni particles were
divorced from the support and encapsulated by many layers of graphitic
carbon. Xiao et al. [7] showed that reactant could not access to Ni metal
encapsulated in carbon, which hence ceased the reaction. Thus, the
sharply decreased H2 production and the forced stopped reaction in
short time on Ni-CeLa0.2-IMP can be explained. For the spent catalysts of
Ni-La2O3 and metal doped samples (Ni-CeLa0.2, Ni-CeTb0.2 and
Ni-CeZr0.2), no obvious cover of Ni particles by carbon was observed,
only some Ni particles on the tip of filamentous carbon were detected.
These results suggest that coking was greatly suppressed by the intro­
duction of La, Tb, or Zr element. Moreover, the small size of Ni particles
was still maintained.
Filamentous carbon with the shape of nanotube could be observed in
Fig. S14. The spent Ni-CeO2 and Ni-CeLa0.2-IMP possessed many carbon
nanotubes (Fig. S14). In comparison, the carbon nanotubes on the spent
Ni-CeLa0.2 were much less. The results demonstrate that the catalyst
doped by La and prepared by the SG method could effectively suppress
carbon deposition, which is confirmed by TEM (Fig. S13) and XRD
(Fig. 8) analyses.
TG was adopted to identify the type and amount of carbon in the
spent catalysts. The TG curves (Fig. 9a) of the spent catalysts showed a
slightly rise in the temperature range of 300 ◦ C–400 ◦ C, which was
caused by the oxidation of the metallic Ni and Ce3+ [44]. The initial
oxidation of carbonaceous deposits happened at around 350 ◦ C, and no
further mass change was detected under the temperature of above 750
◦
C. The rate of carbon deposition was calculated, and the results are
listed in Fig. 9a. The rates of carbon deposition on different catalysts are
in the following order: Ni-CeLa0.2 < Ni-CeZr0.2 < Ni-CeTb0.2 < Ni-CeO2
< Ni-La2O3 << Ni-CeLa0.2-IMP. Compared with Ni-CeO2, the intro­
duction of another metal (La, Tb, Zr) dopant effectively decreased the
coke deposition rate. In particular, the rate of carbon deposition on
Ni-CeLa0.2 was only 0.48 mgc/gcat h, which is less than one fifth of that
on Ni-CeO2 (2.60 mgc/gcat h). The coke deposition rate on Ni-Ce­
La0.2-IMP (212 mgc/gcat h) was 441 times that of Ni-CeLa0.2 (0.48
mgc/gcat h), which can be explained by the bad dispersion of Ni in
Ni-CeLa0.2-IMP that accelerated coke formation. Previous study showed
that the performance of the catalysts for SRE deteriorated due to serious
carbon deposition [13,51]. Similar situation happened on Ni-Ce­
La0.2-IMP, which leaded to forced stopped reaction in short time and
sharply decreased the reaction activity. These results demonstrate that
coke could be effectively inhibited by the introduction of anther metal
(La, Tb, Zr) into Ni-Ce solid oxide using the SG method, which attributes
to the promoted dispersion of Ni, suitable metal-support interaction,
abundant oxygen vacancies and facilitated water dissociation.
To differentiate the carbonaceous deposits, the derivative of the TG
curves was calculated, and the obtained DTG profiles are shown in
Fig. 9b. The two peaks could be assigned to the oxidization of two types
of carbon species [13]. The lower oxidation temperature of coke (α) is
due to its deposition on metal surface or its amorphous state [6,13]. The
higher oxidation temperature of coke (β) is ascribed to the presence of
crystalline carbon such as graphite, carbon nanotube [6]. On Ni-CeO2,
the α peak was mainly detected. Both the peak intensity and peak area
were larger than those of the metal (La, Tb, Zr) doped samples. It in­
dicates substantial coke depositions on metal Ni surface, which caused
severe deactivation. For the catalysts of Ni-CeLa0.2, Ni-CeZr0.2 and
Ni-La2O3, almost no peak appeared at low oxidation temperature.
Moreover, the peak at higher oxidation temperature for Ni-CeLa0.2 was
hardly to be observed, suggesting the small amount of carbon deposited
on the spent catalyst. In comparison, Ni-CeLa0.2-IMP possessed strong
peaks of the two coke species, especially at high temperature. Therefore,
its severe deactivation can be explained by the serious carbon deposition
on catalyst surface.
Moreover, Raman spectra of the spent catalysts were collected, and
the results are shown in Fig. S15. According to Fig. S15a, two obvious
Z. Xiao et al.
Fig. 9. TG/DTG profiles of the spent catalysts.
peaks located at 1337 cm− 1 (D band) and 1590 cm− 1 (G band) are
observed for all the spent catalysts, indicating the coke deposition on
catalyst surface [40]. Compared with Ni-CeLa0.2-IMP, the catalysts
prepared by the SG method possessed weak peak intensities of D band
and G band. Meanwhile, compared with Ni-CeO2, the doping of another
metal (La, Tb, or Zr) effectively decreased the peak intensities of D band
and G band. These results further confirm that metal dopant could
effectively inhibit coke deposition, which is consistent with the previous
TG (Fig. 9) analysis. The Raman spectra relating with oxygen vacancies
were also measured, and the data are depicted in Fig. S15b. Compared
with its fresh state, the spent Ni-CeLa0.2-IMP showed sharply reduced
peak of oxygen vacancies. The oxygen vacancies were maintained well
in the spent catalysts of Ni-CeLn0.2.
Additionally, TPO was also employed to identify the carbon oxi­
dization on the spent catalysts (Fig. S16). Two oxidation peaks at low
temperature and high temperature appeared, which are assigned to two
different coke species [6,7]. Compared with Ni-CeO2, the samples doped
by La, Tb, and Zr possessed sharply decreased peak intensity, suggesting
less coke deposited on their surfaces. Meanwhile, the peaks at high
temperature shifted to lower temperature, indicating that the coke was
more easily oxidized by oxygen. Limited carbon deposition on Ni surface
Scheme 1. Schematic illustration of ethanol steam reforming over the catalysts of Ni-CeLa0.20, Ni-CeO2 and Ni-CeLa0.20-IMP.
11
Applied Catalysis B: Environmental 286 (2021) 119884
was maintained throughout the stability test to achieve high ethanol
conversion and H2 production.
4. Discussion
Based on the results of catalyst structure, DFT simulation and cata­
lytic performance, the mechanisms of long-term SRE reaction on Ni-
CeO2, Ni-CeLa0.2 and Ni-CeLa0.2-IMP are proposed in Scheme 1. The
incorporation of La into Ni-CeO2 solid oxide increased oxygen vacancies
in the catalyst (Figs. 4 and S8c and d, and S9) [1,28]. The oxygen va­
cancies helped to activate water for the generation of many OH groups
and inhibit the dehydrogenation of CH4 (Eq. (5)) and the accumulation
of carbon deposition [1,13,36]. Therefore, the existence of abundant
oxygen vacancies in the reforming catalyst endowed it high capacity of
H2 production (Figs. 6,7, S11, and Table S1) and superior stability with
less coke deposition (Fig. 9, Figs. S15 and S16). The existence of La in the
ceria support also helped to improve the dispersion of metallic Ni par­
ticles (Fig. 2 and Table 2). The small Ni nanoparticles interacted strongly
with the La-doped ceria support, which were active and stable (Figs. 2
and 3). The highly dispersed Ni nanoparticles provided more active
metallic sites (Table 2) and abundant metal-support interfacial sites,
Z. Xiao et al.
which are available for activating reactants [42,50]. Moreover, the
sintering of metal Ni was effectively suppressed by their strong inter­
action with the support (Figs. 1 and 3). Therefore, high ethanol con­
version and hydrogen production rate were achieved on Ni-CeLa0.2. DFT
calculations showed that the presence of doped Ni and La plays a crucial
role in dissociating water and generating abundant surface hydroxyl
groups, which should be one of the origins of high activity and stability.
In comparison, Ni-CeLa0.2-IMP possessing relatively low Ni dispersion
and weak metal-support interaction showed bad SRE performance,
though rich oxygen vacancies were present. The large Ni particles
(Table 2 and Fig. 2) were less active and easily coked (Fig. 9, Figure S13,
S15 and S16). Moreover, the weak metal-support interaction (Fig. 3)
leaded to serious Ni sintering, and the Ni particles were easily departed
from the support (Fig. S13). Then, serious deterioration of Ni-Ce­
La0.2-IMP was observed in a short period of time (Fig. 7).
5. Conclusions
To summarize, metal (La, Tb, Zr)-doped ceria supported Ni catalysts
(Ni-CeLn0.2) have been successfully synthesized by the SG method and
applied for hydrogen production by SRE. Various characterization
techniques were employed to explore the relationship between catalyst
structure and its catalytic performance. High Ni surface area and
enhanced metal-support interaction were achieved on the catalysts
prepared by the SG method compared with the IMP method. Moreover,
the doping of another metal (La, Tb, Zr) into ceria could increase the
concentration of oxygen vacancies and maintain the high dispersion of
Ni by the facilitated metal-support interaction. La-doped ceria supported
Ni prepared by the SG method exhibited high performance for SRE. The
high SRE performance for La-doped ceria supported Ni was explained by
DFT simulation. Remarkably reduced formation energy of oxygen va­
cancies was achieved on Ni and La co-doped ceria (-0.96 eV). In addi­
tion, the dissociation of water is facilitated on Ni and La co-doped ceria.
The water dissociation energy on Ni and La co-doped ceria is -0.25 eV
which is much lower than that on bare ceria (-0.01 eV). Consequently,
the catalyst of Ni-CeLa0.2 provided high hydrogen production rate
(8057.3 μmol/min) without any activity loss during the 3000 min test
under the water to carbon mole ratio of 2 and GHSV of 55920 mL/gcat∙h.
In comparison, Ni-CeLa0.2-IMP seriously deteriorated in 120 min. In
addition, the rate of carbon deposition on Ni-CeLa0.20 was sharply
reduced to only 0.48 mgc/gcat h compared with that on Ni-CeLa0.20-IMP
(212 mgc/gcat h) and Ni-CeO2 (1.62 mgc/gcat h).
CRediT authorship contribution statement
Zhourong Xiao: Conceptualization, Data curation, Formal analysis,
Investigation, Methodology, Resources, Software, Visualization, Writing
- original draft, Writing - review & editing. Chan Wu: Data curation,
Formal analysis, Investigation, Methodology. Li Wang: Methodology,
Resources, Writing - review & editing, Supervision, Funding acquisition.
Jisheng Xu: Methodology, Software, Formal analysis. Qiancheng
Zheng: Methodology, Software, Formal analysis. Lun Pan: Methodol­
ogy, Formal analysis, Supervision. Jijun Zou: Methodology, Formal
analysis, Supervision. Xiangwen Zhang: Methodology, Resources,
Writing - review & editing, Supervision, Funding acquisition. Guozhu
Li: Methodology, Validation, Formal analysis, Investigation, Data
curation, Writing - review & editing, Supervision, Funding acquisition.
Declaration of Competing Interest
The authors report no declarations of interest.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.apcatb.2021.119884.
12
Applied Catalysis B: Environmental 286 (2021) 119884
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