Renewable Energy 145 (2020) 1507e1516

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Efficient syngas production via dry reforming of renewable ethanol

over Ni/KIT-6 nanocatalysts
Yichen Wei a, Weijie Cai a, *, Shiji Deng a, Zhongcheng Li b, Hao Yu c, Shaoyin Zhang a,
Zhihui Yu a, **, Li Cui a, Fengzuo Qu a, ***
a
Faculty of Light Industry and Chemical Engineering, Dalian Polytechnic University, 116023, Dalian, China
b
Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, College of Chemistry and Molecular Engineering, Qingdao
University of Science and Technology, 266042, Qingdao, China
c
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, 266590, Qingdao, China

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a Ni/KIT-6 catalyst with the highly uniform Ni dispersion was synthesized by a facile
Received 19 December 2018 methanol-assisted co-impregnation technique and its activity towards to CO2 reforming of renewable
Received in revised form ethanol was depicted for syngas production and CO2 elimination. Herein, its physicochemical features
12 June 2019
were determined in detail by various characterization technique including XRD, TPR, Raman, SEM and
Accepted 15 July 2019
TEM etc. The results revealed the presence of the smaller Ni particles and the stronger Ni-support
Available online 16 July 2019
interaction in the Ni/KIT-6 catalyst compared to the reference Ni/SiO2 sample. More importantly, Ni/
KIT-6 catalyst showed the satisfactory activity and stability while a rapid deactivation was noted for
Keywords:
Syngas
Ni/SiO2. Typically, full ethanol conversion was obtained at 550
C for Ni/KIT-6 and no obvious deacti-
Ethanol dry reforming vation was observed after 40 h tests. Indeed, this superior behavior was related to the confinement effect
Ni/KIT-6 of KIT-6 channels which could stabilize Ni particles under the severe reaction conditions. On the other
Stability hand, the smaller Ni species greatly inhibited the coke deposition, especially for the encapsulated carbon.
Metal-support interaction Moreover, the existence of strong Ni-support interaction was also responsible for the anti-sintering of
active metal and carbon accumulation. This attractive results might be helpful to design high efficient Ni-
based catalysts for chemical conversion of the undesirable CO2.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction feedstocks to synthesize liquid fuels and high-valued chemicals via

Up to date, chemical conversion of the undesirable carbon di-
oxide (CO2), a greenhouse gas, has been of great interest to meet
with the sustainable development. Among the developed routes,
CO2 reforming of renewable ethanol is viewed as an promising
process for syngas production instead of conventional methane dry
reforming [1,2]. In addition, the rapid growth of second generation
ethanol from inedible lignocellulose resources could significantly
stimulate this sustainable approach [3,4]. Apart from environ-
mental protection, ethanol dry reforming might yield a suitable
syngas ratio (H2/CO ¼ 1/1), which could be directly selected as
* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: caiwj@dlpu.edu.cn (W. Cai), zhi_hui_yu@163.com (Z. Yu),
qufz@dlpu.edu.cn (F. Qu).
Fischer-Tropsch synthesis (FTS) [5e7]. To the best of our knowl-
edge, research on CO2 reforming of ethanol is still in the infancy.
Herein, the design and/or development of high efficient catalysts
for this attractive process remains a great challenge.
Dry reforming reaction is normally carried out under higher
temperature regions due to its highly endothermic properties.
Hence, this tended to cause the quick deactivation because of the
active metal sintering and coke accumulation over the catalyst
surface [8]. In the last several decades, noble metal based catalysts
including Rh, Pt, Ir and Pd etc have been investigated for syngas
production from dry reforming process, which have demonstrated
good resistance to metal aggregation and/or carbon formation,
thereby leading to the better activity and stability [9e12]. Unfor-
tunately, the less availability and higher cost retarded their wide
application in pilot scale. To address this drawback, much work
have focused on transition metal based catalysts especially Ni cases
considering its less cost and comparable performance in

https://doi.org/10.1016/j.renene.2019.07.077
0960-1481/© 2019 Elsevier Ltd. All rights reserved.
1508 Y. Wei et al. / Renewable Energy 145 (2020) 1507e1516
comparison with noble metals [13e15]. However, despite its
desirable capacity of C-C bond dissociation, the industrial applica-
tion of Ni-based samples is still limited owing to its relatively less
stability [16]. Herein, Hu et al. depicted that Ni/Al2O3 catalyst
exhibited the good activity, selectivity for ethanol dry reforming
while it suffered from the quick deactivation [17]. Additionally,
Zawadzki et al. also elucidated the prone deactivation of Ni cata-
lysts under the severe conditions of ethanol dry reforming [18].
Interestingly, great efforts have been devoted to improve the
stability of Ni catalysts via different ways such as incorporation of
additives [19e21], confinement of Ni species within ordered
structure [22,23] and the utilization of suitable supports [24]. In
particular, one of the attractive strategies was to controllably de-
posit Ni species over the typical supports with high surface area
and/or uniform framework in order to enhance the dispersion of
the active metal [25,26]. In addition, the existence of strong metal-
support interaction (SMSI) could also improve thermal stability and
the capacity for carbon cleaning. So far, numerous ordered silica
such as MCM-41, KIT-6, SBA-15 and HMS etc have been selected as
support candidates for Ni-based catalysts [27e30]. Liu et al.
revealed that Ni/MCM-41 presented the satisfactory activity in
methane dry reforming and MCM-41 support was considered as
one of the key factors to inhibit metal sintering and coke deposition
because of the confinement effect [31]. Qiu et al. proposed SBA-15
as a desirable support for methane dry reforming, which might
efficiently stabilize the active species [32].
Indeed, rare investigation have been conduced on ethanol dry
reforming over Ni-based catalyst with ordered silica as support. In
this sense, KIT-6 provided several unique properties including
tunable structure with interconnected pores, large surface area and
thick pore walls with high thermal stability etc [33,34]. More
importantly, its specific three-dimensional (3D) cubical channels
was favorable for the diffusion of reactant gas, thereby presenting
higher activity compared to other silica support with 2-D hexago-
nal structure [35].
To address this issue, Ni/KIT-6 catalyst was synthesized by a
methanol-assisted co-impregnation technique. In addition, its
catalytic activity/stability in ethanol dry reforming was determined
in detail. In particular, methanol could facilitate the targeted Ni
species to enter into KIT-6 channels via capillary force and upon
evaporating, methanol was adsorbed onto the internal surface of
silica support, thereby inhibiting the aggregation of Ni particles.
Moreover, a comparison was conducted with a reference Ni/SiO2
catayst supported on commercial silica in order to clearly depict the
confinement effect of KIT-6 support. The as-prepared Ni/KIT-6
catalyst was further characterized by BET, H2-TPR, XRD, Raman and
SEM to analyze its physicochemical properties. The main purpose of
this current work is to develop the efficient catalyst system for
ethanol dry reforming to simultaneously produce value-added
syngas and eliminate the undesirable CO2.
2. Experimental
2.1. Synthesis of KIT-6 support
KIT-6 support was prepared as illustrated in the previous liter-
ature [36]. Firstly, 6.0 g of Polyether P123 (Polyethylene-poly-
propylene glycol, Macklin) was dissolved into a mixture of 11.8 g
concentrated HCl (36 wt%) and 217 g deionized (DI) water at room
temperature, and the solution was then magnetically stirred for 1 h.
Subsequently, 6.0 g of n-butanol was added into the solution and
another stirring was conducted for 1 h at 40
C. After the addition of
12.9 g tetraethoxysilane (TEOS), the mixture was further stirred for
24 h at 40
C. The achieved mixture was then transferred into an
autoclave and kept at 100
C for 24 h. The filtered precipitate were
thoroughly washed by hot water, and then dried overnight at
100
C. Finally, the powder was calcined at 550
C for 6 h in static
air.
2.2. Preparation of Ni-based catalysts
A mixture containing Ni(NO3)3$6H2O precursor and support
(KIT-6 or commercial SiO2) were added to a methanol solution, and
then it was magnetically stirred at 60
C until the complete evap-
oration of methanol. The obtained powder was dried overnight at
90
C and then calcined at 600
C for 6 h in static air. The as-
prepared catalysts were labeled as Ni/KIT-6 and Ni/SiO2,
respectively.
2.3. Catalyst characterization
The actual loadings of Ni species were determined by an
inductively coupled plasma atomic emission spectrometer (ICP-
AES) (PerkinElmer, Optima 8000).
The specific surface areas and the distribution of pore size were
obtained by N2 adsorption-desorption measurements at 196
C
using an ASAP 2010 Micrometrics apparatus.
X-ray diffraction (XRD) was carried out on a Shimadzu XRD-
7000S apparatus to analyze the crystalline structures of the as-
prepared catalysts. The average particle sizes were calculated ac-
cording to Debye-Scherrer equation.
Hydrogen temperature programmed reduction (H2-TPR) was
performed on a Micromeritics AutoChem II chemisorption instru-
ment to distinguish the catalyst reducibility. Prior to measurement,
catalyst was pretreated at 200
C for 1 h under a N2 flow (30 mL/
min) and then cooled down to room temperature. After that, a 5 vol
% H2/N2 flow (20 mL/min) was injected and temperature was then
increased to 800
C with a heating rate of 10
C/min.
The morphology of the catalyst was analyzed by scanning
electron microscope (SEM) on a JSM-7800F apparatus equipped
with an X-ray energy dispersive spectrometer (X-Max50).
Transmission electron microscopy (TEM) was conducted using a
JEM-2100 equipment operated at 200 kV to probe morphology
structure of the spent catalysts.
The size distribution of the as-prepared catalyst were deter-
mined on a laser scattering particle size analyzer (Malvern, nano-
ZS90).
Raman spectra were recorded using a RENISHAW inVia Raman
Microscope equipped with a charge-coupled-device (CCD) detector.
2.4. Catalytic tests
CO2 reforming of ethanol reactions were conducted in a fixed-
bed micro-reactor with a stoichiometric feedstocks (CO2/
ethanol ¼ 1/1, molar ratio) and testing temperature region from
400 to 600
C. Prior to tests, 75 mg catalysts (40-60 mesh) were in-
situ reduced at 600
C for 1 h under a flow of 5 vol% H2/N2 (30 mL/
min). Reactant ethanol was injected into a vaporizer (210
C) using
a micro-pump (Series III type) and the formed steam were thor-
oughly mixed with the flow of CO2 and N2 which were precisely
controlled by mass-flow controllers (ethanol/CO2/N2 ¼ 1/1/2, molar
ratio). Inert gas N2 (25 mL/min) was selected as diluted gas and
internal standard gas. The total gas hourly space velocity (GHSV)
including the injected N2 flow was set at 40,000 mL g1 1
cath . The
effluent was continuously monitored online by a gas chromato-
graph (GC) equipped with TCD and FID detectors. Moreover, part of
catalytic tests were repeated at least twice and the deviation of the
results were within 5%, thereby indicating the relatively repro-
ducibility of the experiments.
Ethanol conversion and the molar concentration of the product
 Y. Wei et al. / Renewable Energy 145 (2020) 1507e1516 1509

in the outlet gas was calculated as following:

F Inlet Oulet
EtOH  F EtOH
XEtOH ¼ (1)
F Inlet
EtOH

x
Yx ¼ P Outlet (2)
xOutlet

where xoutlet was the molar concentration of the detected product,

including H2, CO, CH4, CH3COCH3 and CH3CHO.

3. Results and discussion

3.1. Textural properties of the catalysts

As listed in Table 1, the actual Ni contents were close to the

nominal ones in all cases. Hence, it was reasonable to compare the
catalytic behavior of Ni/KIT-6 and Ni/SiO2. The specific surface area
of the synthesized KIT-6 support was ca.733 m2/g. After the Fig. 1. N2 adsorption-desorption isotherms of KIT-6 and Ni/KIT-6 catalyst.

impregnation of Ni species, surface area remarkably decreased to

497 m2/g, implying the pore blockage by the Ni particles. Notice-
H2-TPR profiles of the investigated catalysts are recorded to
ably, the decline of pore volume for Ni/KIT-6 further evidenced the
distinguish the catalyst reducibility and the interaction between
incorporation of Ni species into the pore structure of KIT-6 support,
active Ni species and support. As depicted in Fig. 3, there was only
which was in accordance with the previous reports [37,38].
one sharp reduction peak at around 372.
N2 adsorption-desorption isotherms are shown in Fig. 1. It was o
C was observed for Ni/SiO2 sample. This generally corre-
noteworthy that the isotherm of KIT-6 support clearly showed type
sponded to the reduction of bulk NiO, which possessed the slight
IV curves with the H1 hysteresis loop suggesting the mesoporous
interaction with silica support. On the contrary, a relatively sharp
structure according to the IUPAC nomenclature [39]. More impor-
peak at ca. 349
C and a broad band near 555
C were noted for Ni/
tantly, the observed hysteresis loop of Ni/KIT-6 was narrower which
KIT-6 catalyst. As discussed in the previous literature [40,43,44], the
was probably attributed to the incorporation of Ni species in KIT-6
first peak was attributed to the reduction of larger Ni particles and/
support [40]. This finding depicted that the impregnation of Ni
or the NiO species locating on the external surface of support. On
species partly destroyed the mesoporous structure of KIT-6 sup-
the other hand, H2 consumption at higher temperature region was
port. As presented in Fig. 1, the pore size distribution of KIT-6
assigned to the reduction of the smaller NiO particles with a strong
support was in the range of 2.5e6 nm. In contrast, the value of
metal-support interaction. Hence, it could be concluded that Ni/
Ni/KIT-6 catalyst decreased to 1.5e5 nm, indicating the successful
KIT-6 catalyst possessed small-sized NiO species and the stronger
incorporation of Ni nanoparticles in frame structure of KIT-6. In
Ni-support interaction, which was critical to improve catalyst sta-
conclusion, the visible decline of specific surface area and pore
bility. The results were in good line with the XRD findings. Wang
volume was assigned to the existence of Ni particles in the channels
et al. also proposed that the stronger metal-support interaction
of KIT-6 support.
could significantly retard the aggregation of active Ni metal and
The wide-angel XRD patterns of the Ni-based catalysts (Ni/KIT-6
enhance its stability [45].
and Ni/SiO2) are depicted in Fig. 2. In particular, a broad diffraction
FESEM micrographs and elemental mappings of the as-prepared
band located at ca.15-30
was observed corresponding to the short-
catalyst are shown in Fig. 4. SEM images elucidated that both the
range ordered structure of silica. Additionally, the peaks at around
shapes and the particle sizes of the Ni/SiO2 sample were irregular.
37.2
, 43.4
and 62.9
were attributed to the (111), (200) and (220)
Additionally, the obvious aggregation of nanoparticles was noted.
crystalline planes of cubic NiO phase (JCPDS 44-1159) [41,42]. As
On the contrary, Ni/KIT-6 catalyst presented a spherical
illustrated in Table 1, the average particle size of Ni/KIT-6 was
morphology with the size in the region of 1e3 mm, in accordance
ca.11 nm which was less than that of Ni/SiO2 (15 nm). This finding
with the size of KIT-6 [46]. Interestingly, the results of dynamic light
pointed out the higher dispersion of Ni species in Ni/KIT-6 catalyst
scattering measurement (Fig. 4g) indicated that the average
due to the confinement effect of its ordered channels. It was
diameter of Ni/KIT-6 particle was ca.1.4 mm, which was in line with
accepted that the smaller Ni particles generally possessed a higher
the SEM findings. Noticeably, the Ni modified catalyst presented
saturation concentration of coke and herein a lower driving force
some rock-like particles on the whole KIT-6 support surface. These
for coke diffusion over Ni particles, which could inhibit carbon
Ni particles might contribute to the first reduction peak as observed
formation.

Table 1
Textural features of the as-prepared catalysts.

Catalyst SBET (m2/g) Pore volume(cm3/g) Ni sizea (nm) Ni sizeb (nm) Ni contentc (wt%)

KIT-6 733 0.59 - - -

Ni/KIT-6 497 0.41 11 14 13.9
Ni/SiO2 113 0.87 15 20 14.3

The average sizes of Ni particles were calculated according to Debye-Scherrer's equation.

a
Fresh catalyst.
b
Spent catalyst.
c
Obtained from ICP-AES results.
1510 Y. Wei et al. / Renewable Energy 145 (2020) 1507e1516
Fig. 2. XRD patterns of the investigated catalysts: (a) fresh and (b) used.
Fig. 3. H2-TPR profiles of the fresh Ni/KIT-6 and Ni/SiO2 catalysts.
in H2-TPR analysis. In addition, elemental mapping images of Ni
species were recorded to determine its existence and dispersion.
The results (Fig. 4f) indicated the high dispersion of Ni species for
Ni/KIT-6 catalyst while the relatively less dispersion was noted for
Ni/SiO2 sample. It was accepted that the uniform distribution of
active metal was favorable to improve the catalyst activity and
stability.
3.2. Catalytic tests
3.2.1. Effect of temperature
Ethanol conversion and molar concentration of the product in
the outlet dry gas over pure KIT-6 support, Ni/KIT-6 as well as the
blank tests are depicted in Fig. 5 for comparison. As expected, a
similar ethanol conversion (ca.11%) was noted for KIT-6 support and
blank experiments due to the inert property of silica. On the con-
trary, in the presence of Ni species (Ni/KIT-6), ethanol conversion
remarkably increased to ca. 65% as well as the anti-formation of
byproduct acetone. This finding illustrated that the homogeneous
CO2 reforming of ethanol was negligible and dry reforming reaction
mainly occurred over active sites and/or metal-support interface.
The effect of reaction temperature on catalyst activity was
examined within the temperature region of 400e600
C. Typically,
catalytic tests were conducted under the stoichiometric feed ratio
(ethanol/CO2 ¼ 1/1, molar ratio). As depicted in Fig. 6, ethanol
conversion was clearly enhanced with increasing temperature and
full conversion was obtained at 550
C for Ni/KIT-6 catalyst. By
contrast, complete ethanol conversion was achieved at 600
C for
reference Ni/SiO2. During the whole temperature region, Ni/KIT-6
still presented higher ethanol conversion in comparison with the
analogous Ni/SiO2 sample. This beneficiation was attributed to its
smaller Ni particles considering the comparable concentrations of
Ni species in two catalysts. As already mentioned, the smaller
particle size could provide more active sites to achieve the better
activity. Silva group [47] pointed out that catalytic activity greatly
relied on the amount of active sites. Thermodynamic calculation
revealed that 100% ethanol conversion was anticipated over the
whole testing temperature range [48]. Hence, the observed partial
conversion of ethanol indicated that dry reforming reaction took
place under kinetic control region, which normally resulted in the
appearance of the undesirable products such as acetone. On the
other hand, conversion of another reactant CO2 was negative below
450
C, implying that CO2 conversion was slower than its forma-
tion. This could be explained by the Boudouard reaction toward the
preferable production of CO2 (2CO / CO2 þ C). This observation
was also evidenced by the theoretical calculation from Jankhah
et al. [49]. Further increasing temperature led to the improvement
of CO2 conversion. This was caused by the combination effect of
methane dry reforming (CH4 þ CO2 / 2CO þ 2H2) and the reverse
Boudouard reaction (C þ CO2 / 2CO), which were thermody-
namically favorable at higher temperature. This was further veri-
fied by the increase of CO molar concentration and the decline of
methane selectivity. CH4 formation was assigned to the direct
thermal cracking of ethanol. Moreover, the decrease of H2 selec-
tivity at 450
C might be attributed to the occurrence of methana-
tion reaction (CO2 þ 2H2 / CH4). On the contrary, the observed
decline at 600
C was probably due to the reverse gas shift reaction
(CO2 þ H2 / CO þ H2O) based on the thermodynamic considering.
Simultaneously, higher reaction temperature also prevented the
formation of byproduct acetone.
Another interesting notification was that the molar concentra-
tions of the targeted products (H2 and CO) for Ni/KIT-6 were larger
than those obtained over the reference Ni/SiO2, as well as a
consequence of less formation of side-products (CH4 and/or
acetone). This finding evidenced the attractive behavior of Ni/KIT-6
 Y. Wei et al. / Renewable Energy 145 (2020) 1507e1516 1511

Fig. 4. SEM and elemental mapping images of catalysts. (a-c) Ni/SiO2; (d-f) Ni/KIT-6; (g) size distribution of Ni/KIT-6 determined from dynamic light scattering (DLS).
1512 Y. Wei et al. / Renewable Energy 145 (2020) 1507e1516

Fig. 5. Comparison of ethanol dry reforming over Ni/KIT-6, KIT-6 and blank catalysts
(SiC). (Reaction conditions: Ethanol/CO2 ¼ 1/1, molar ratio; T ¼ 450
C,
GHSV ¼ 40,000 mL g1 1
cath ).

sample in syngas production from ethanol dry reforming. In addi-

tion, the achieved H2/CO ratio was close to 1 at 600
C for Ni/KIT-6
catalyst, which was suitable for Fischer-Tropsch process. Notice-
ably, the highest methane yield was observed at 450
C. This result
implied that the occurrence of methanation reaction (CO2 þ 2H2 /
CH4) was preferable than methane dry reforming (CH4 þ CO2 /
2CO þ 2H2), which was normally operated at the high temperature
region.

3.2.2. Effect of CO2/ethanol ratio

The impact of CO2 concentration on ethanol conversion and
product distribution was further checked at 550
C. As depicted in
Fig. 7, the ratio of CO2/ethanol obviously played an important role in
ethanol dry reforming. More importantly, increasing CO2 concen-
tration enhanced ethanol conversion and complete conversion was
achieved under CO2/ethanol ratio of 1, thereby reaching thermo-
dynamic equilibrium level. This positive effect of CO2 on ethanol
conversion was in line with the previous findings [17,21]. Indeed,
the excess CO2 could accelerate the reaction rate of secondary
methane dry reforming to convert intermediates CH4 into the tar-
geted syngas. In fact, the substantial increase of H2 and CO con-
centration in the outlet gas were also noted with the presence of
more CO2. Additionally, the ratio of CH4/CO was below 1.0 indi-
Fig. 6. Effect of reaction temperature on ethanol dry reforming over Ni-based catalysts.
cating the occurrence of methane dry reforming as already pointed
(Reaction conditions: Ethanol/CO2 ¼ 1/1,molar ratio; GHSV ¼ 40,000 mL g1 1
cath ).
out by Foo et al. [50]. Thermodynamic analysis also proposed that
ethanol dry reforming was favored at the higher ratio of CO2/
ethanol [49]. reaction. On a further increase of CO2 concentration, CH4 yield
In addition, the reaction results in Fig. 7 were further compared decreased and tended to be much closer to thermodynamics. At the
with the thermodynamic values reported by Jankhah group [49] so largest CO2/ethanol ratio (2/1), the decline of H2 yield along with
as to check how far ethanol conversion and product molar con- the increase of CO selectivity was attributed with the preferable
centrations were close to thermodynamics. The partial ethanol occurrence of the reverse water gas shift reaction.
conversion in the lower CO2/ethanol ratio domain revealed that
ethanol conversion was kinetically controlled, as depicted in our
previous literature [51]. Indeed, experimental H2 molar concen- 3.2.3. Stability test
tration was always larger than the values at thermodynamic equi- From the standpoint view of pilot scale application, it was crit-
librium. This might be caused by the fact that carbon sequestration ical to design an highly active and stable catalyst for value-added
shifted the equilibrium [49]. Meanwhile, the larger experimental syngas production from ethanol dry reforming. Therefore, the
yield of CO evidenced that the Boudouard reaction probably was long-term stability tests of Ni-based catalysts were executed at
not being at equilibrium, giving more CO than predicted by ther- 550
C for 40 h under the stoichiometric feedstocks (ethanol/CO2
modynamic calculation. On the other hand, the heavier production ratio ¼ 1, molar ratio). As presented in Fig 8, in the case of Ni/KIT-6
of CH4 than the values in thermodynamic equilibrium confirmed catalyst, no obvious fluctuation of ethanol conversion and H2/CO
that methane dry reforming was a slow and energy demanding ratio was observed during the whole testing period, thereby
 Y. Wei et al. / Renewable Energy 145 (2020) 1507e1516 1513

unchanged and the negligible acetone was detected. On the con-

trary, Ni/SiO2 sample suffered from the quick deactivation during
the stability test. Herein, ethanol conversion sharply declined from
100% to 38% after the initial running of 5 h. In particular, the
appearance of more acetone (from 0.5mol% to 14mol%) indicated
that the capacity of C-C bond dissociation for Ni/SiO2 significantly
declined and ethanol was preferably converted into acetone via
aldolization process instead of the direct decomposition into CO,
CH4 and H2. More importantly, the ratio of H2/CO increased from 1.5
to 1.9, which was due to the water gas shift reaction. This fluctua-
tion was also attributed to the suppression of coke elimination
reaction (C þ CO2 / 2CO) and led to carbon accumulation over
catalyst surface, thereby causing catalyst deactivation. This was in
good line with the previous findings [52]. In conclusion, the as-
prepared Ni/KIT-6 catalyst exhibited the superior catalytic activity
and stability for ethanol dry reforming.

Fig. 7. Effect of CO2/ethanol ratio on the activity of Ni/KIT-6 catalyst. (Reaction con- 3.3. Characterization of spent catalyst
ditions: T ¼ 550
C, GHSV ¼ 40,000 mL g1 1
cath ).

Generally, the sintering of Ni particles and coke deposition

resulted in the deactivation of Ni-based catalysts. To address this
confirming its attractive stability. In addition, the calculated C
issue, the aged Ni/SiO2 and Ni/KIT-6 catalysts were characterized in
balance was above 93%, which evidenced the reliability of the tests.
detail using XRD, Raman and TEM. Particularly, new diffraction
The promising stability was probably attributed to the smaller Ni
bands corresponding to metallic Ni0 species (JCPDS 04-0850)
nanoparticles and the stronger metal-support interaction in Ni/KIT-
appeared in XRD patterns (Fig. 2b). The presence of metallic Ni after
6 catalyst which were mentioned in XRD and TPR findings. These
stability tests might be caused due to the reduction atmosphere
beneficial factors could stabilize the Ni species via Si-O-Ni-O-Si
with the presence of H2 and CO. Additionally, a small shoulder band
bond to inhibit its sintering during the reaction and thereby
corresponding to NiO species was observed because of the ex-situ
maintain the activity. Meanwhile, the formed methane remained
catalyst re-oxidation. Noticeably, the intensity of this shoulder
peak for Ni/SiO2 was less, implying that the formed coke over Ni/
SiO2 surface which acted as a protecting layer could prevent the re-
oxidation of the spent catalyst [53]. On the other hand, the
diffraction peaks of Ni0 species for the spent Ni/SiO2 was sharper,
which demonstrated its larger particle size due to the aggregation.
As listed in Table 1, the average Ni crystal sizes of Ni/SiO2 increased
from 15 to 20 nm after stability test while only a slight sintering
from 11 to 14 nm was noted for the aged Ni/KIT-6. This superior
anti-sintering property of Ni/KIT-6 was attributed to the confine-
ment effect of the KIT-6 pores and the stronger Ni-support inter-
action as elucidated in H2-TPR profiles. Indeed, the strong metal-
support interaction facilitated the formation of smaller particles
by stabilizing metal particles.
The types of carbonous deposits are also determined by Raman
analysis and the recorded spectra are shown in Fig. 9. In all cases,

Fig. 8. Stability tests for ethanol dry reforming over Ni/KIT-6 catalyst. (Reaction con-
ditions: T ¼ 550
C; Ethanol/CO2 ¼ 1/1, molar ratio; GHSV ¼ 40,000 mL g1 1
cath ). Fig. 9. Raman spectrum of the spent catalysts.
1514 Y. Wei et al. / Renewable Energy 145 (2020) 1507e1516
Fig. 10. TEM images of the spent catalysts: (a-b) Ni/SiO2; (c-e) Ni/KIT-6.
two discrete peaks at 1342 and 1592 cm1 were observed, which
corresponded to D band and G band, respectively. Typically, D band
was assigned to the breathing modes (A1g) of rings in amorphous
carbon or defective nanofibers while G band was related to C-C
stretching vibrations (E2g) of C sp2 atoms in graphite layers [18]. The
observation of G band generally revealed the formation of ordered
coke, which was regarded as the deactivated coke. Hence, this
finding clarified the heterogeneity feature of the accumulated coke
over catalyst surface. Indeed, Zawadzki et al. depicted that the
amorphous coke originated from the ethylene polymerization and/
or methane decomposition (CH4 / C þ H2) could lead to the for-
mation of crystalline carbon [18]. The ratio of peak area for Ni/SiO2
and Ni/KIT-6 was around 1.25 suggesting that more coke was
formed for Ni/SiO2 catalyst. Moreover, the peak intensity of G band
in Ni/KIT-6 catalyst was relatively less in comparison with Ni/SiO2,
implying the less deposition of ordered carbon over the Ni/KIT-6
surface. Apparently, both the smaller Ni particles and/or stronger
Ni-support interaction contributed to this carbon depression.
Hence, the resistance to coke formation might partly explain the
high stability of Ni/KIT-6 catalyst.
It was accepted that the graphite type coke could result into
catalyst deactivation. This kind of coke covered the active metals
and thereby retarded the contact between the active sites and the
reactants [54]. Herein, the integrated area ratio of D and G band (IG/
ID) might be selected as a indicator to indirectly reflect the crys-
tallization degree of carbon. Generally, the larger ratio corre-
sponded to the higher graphitization degree. In the current work,
the calculated IG/ID ratios obeyed the following tendency: Ni/SiO2
(0.67)>Ni/KIT-6 (0.52). The less amount of ordered coke on Ni/KIT-6
sample was attributed to its smaller Ni particles, as elucidated in
the previous reports [55].
Fig. 10 shows the TEM images of the aged catalysts. It was
noticeable that large amounts of coke were observed over Ni/SiO2
surface and the catalyst particles were enwrapped by the formed
coke in accordance with the findings from Raman analysis. There-
fore, the reactant gas could not access the Ni sites, resulting in the
observed deactivation. On the contrary, most of the observed car-
bon for Ni/KIT-6 catalyst were isolated carbon nanofilaments (CNF).
It was depicted that this kind of the filamentous carbon was not
detrimental for catalyst activity [56]. Indeed, the formation of this
type carbon was inevitable for ethanol dry reforming because
ethanol acted as the coke precursor [57]. In addition, the Ni/KIT-6
surface was relatively clean and only the slight encapsulated coke
was observed (Fig. 10e). Noticeably, catalyst morphology still
maintained sphere shapes without the structure collapse. In
conclusion, the as-prepared Ni/KIT-6 catalyst showed attractive
merits in anti-coke deposition and the prevention of Ni sintering
for ethanol dry reforming.
4. Conclusions
In this work, a Ni/KIT-6 catalyst was synthesized by an
methanol-assisted impregnation technique. Essentially, character-
ization results revealed that the as-prepared Ni/KIT-6 sample hos-
ted the smaller Ni particle sizes and the stronger interaction
between Ni sites and KIT-6 support in comparison with the com-
mercial silica supported Ni/SiO2. Indeed, Ni/KIT-6 showed the
promising activity and stability in ethanol dry reforming. This
 Y. Wei et al. / Renewable Energy 145 (2020) 1507e1516
superior behavior might originate from the synergy effect of the
stronger Ni-support interaction and the confinement impact of KIT-
6 ordered channels, thereby promoting anti-coke deposition and
stabilizing the small Ni species. This potential results might be
meaningful to develop the high efficient Ni-based catalysts for
syngas production from chemical conversion of the undesirable
CO2.
Acknowledgements
This work was supported by Natural Science Foundation of
Liaoning Province (20170540073; 20170520427), General project
from Department of education of Liaoning Province (2017J026) and
National Key R&D Program of China (2017YFB0308701).
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