An active and stable Ni/MMT-AE catalyst for dioctyl phthalate hydrogenation

Article abstract of DOI:10.1016/j.mcat.2020.111156

Several Ni/Montmorillonite (MMT) catalysts were prepared and evaluated in the hydrogenation of dioctyl phthalate to di(2-ethylhexyl) hexahydro-phthalate, an environmentally friendly plasticizer. Notably, a Ni/MMT-AE catalyst, which was prepared by the ammonia evaporation method, showed excellent activity and stability. It could be steadily used ten times under harsh reaction conditions, comparable to most of the noble metal catalysts. TEM results revealed that the active nickel species were highly dispersed on the surface of the MMT support with average particle sizes of 4.1 nm in the Ni/MMT-AE catalyst, resulting in its high activity. XPS and TPR results demonstrated the strong interaction between nickel and the MMT support, which could effectively inhibit the agglomeration and loss of the active nickel species during the reaction, accounting for its outstanding stability.

Full text of DOI:10.1016/j.mcat.2020.111156

Molecular Catalysis 495 (2020) 111156
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
An active and stable Ni/MMT-AE catalyst for dioctyl phthalate
hydrogenation
a
a
a
a
a
b
a,
Shilin Nie , Huafan Li , Jingru Qin , Yansu Wang , Libo Niu , Ligong Chen , Guoyi Bai *
a
College of Chemistry and Environmental Science, Hebei University, Baoding 071002, PR China
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China
b
A R T I C L E I N F O
A B S T R A C T
Keywords:
Several Ni/Montmorillonite (MMT) catalysts were prepared and evaluated in the hydrogenation of dioctyl
phthalate to di(2-ethylhexyl) hexahydro-phthalate, an environmentally friendly plasticizer. Notably, a Ni/MMT-
AE catalyst, which was prepared by the ammonia evaporation method, showed excellent activity and stability. It
could be steadily used ten times under harsh reaction conditions, comparable to most of the noble metal cat-
alysts. TEM results revealed that the active nickel species were highly dispersed on the surface of the MMT
support with average particle sizes of 4.1 nm in the Ni/MMT-AE catalyst, resulting in its high activity. XPS and
TPR results demonstrated the strong interaction between nickel and the MMT support, which could effectively
inhibit the agglomeration and loss of the active nickel species during the reaction, accounting for its outstanding
stability.
Hydrogenation
Dioctyl phthalate
Nickel
Ammonia evaporation method
Stability
Introduction
silica foam catalyst [16]. Xu et al. found the micropore size of support
played an important role in the aqueous-phase hydrogenation of DOP
Plasticizers are indispensable additives in the polymer processing
industry, which can markedly improve the processability, flexibility,
and fluidity of polymers [1,2]. During the processing, heating, trans-
porting, and packaging of foods, phthalate (PAEs) plasticizers, which
are the most widely used plasticizers in the polymer packaging, can
easily penetrate and then enter human body. They may induce diseases
through oxidative damage-mediated mechanisms due to the presence of
phenyl groups and have been confirmed to bring more possibility of
obesity, cancer and other problems due to the attack of the endocrine
system [3–7]. Therefore, an environmentally friendly plasticizer, cy-
clohexane-dicarboxylate esters (CHDE), has attracted more attention in
recent years [8–10]. It has been allowed in some plastics industry, in-
cluding medical devices, toys and food packaging, in many countries to
replace the traditional and harmful phthalates [11,12].
Catalytic hydrogenation of phthalates is the most important and
efficient method to synthesize CHDE (Scheme 1). Considering the
benzyl ring in phthalic acid esters has two moderate electron-with-
drawing ester groups, its hydrogenation usually performs under harsh
reaction conditions over noble metal catalysts [13–15]. For instance,
Lende et al. reported that the complete hydrogenation of dioctyl
phthalate (DOP) to di(2-ethylhexyl) hexahydro-phthalate (DEHHP)
could be significantly improved over a Rh/Al-modified mesoporous
over Ru/AC catalysts [1]. Whereas, the high price and limited resources
of the noble metals restrict their industrial applications. Therefore, it is
of great significance to develop highly efficient and low-cost catalysts
for phthalate hydrogenation.
Nickel-based catalysts have received extensive attention in hydro-
genation, [17,18] dehydrogenation [19,20] and methane reforming
reactions [21,22] due to their good catalytic performance and low cost.
However, there are scant reports on the hydrogenation of phthalates
over nickel-based catalysts, which are mainly attributed to the harsh
reaction conditions arising from the electron-deficient aromatic ring in
2 3
phthalates. Zhao et al. reported that a 60 %Ni/Al O -B catalyst showed
good activity in the hydrogenation of DOP to DEHHP, mainly due to the
highly dispersed nickel, but lack of the stability result [23]. Generally,
the stability of the nickel-based catalysts was not as good as the noble
metal catalysts under harsh reaction conditions due to the aggregation
and leaching of the Ni species [24]. Therefore, fabrication a stable
nickel-based catalyst for the hydrogenation of phthalates is still a great
challenge.
On the other hand, montmorillonite (MMT) is a kind of natural
aluminosilicate, which is composed of two layers of silica tetrahedral
with a layer of aluminum octahedron [25,26]. It has several advantages
such as low price, good mass-transfer efficiency, chemical and heat
⁎
Corresponding author.
E-mail address: baiguoyi@hotmail.com (G. Bai).
https://doi.org/10.1016/j.mcat.2020.111156
Received 28 May 2020; Received in revised form 26 July 2020; Accepted 29 July 2020
2468-8231/ © 2020 Elsevier B.V. All rights reserved.

S. Nie, et al.
Molecular Catalysis 495 (2020) 111156
Preparation of Ni/MMT-DP
3 2 2
In a typical run, 0.99 g of Ni (NO ) ·6H O was dissolved in 34 mL of
deionized water under stirring, followed by the addition of 1.0 g of
MMT. Then, 1.0 M NaOH solution was dropwise added to adjust the pH
value of the suspension to 11−12. Subsequently, the suspension was
stirred at 40 °C for 4 h and then aged for 8 h. After that, the suspension
was filtered, washed with deionized water to pH = 7–8, followed by
three times of washing with ethanol and then dried at 80 °C for 12 h.
The resulting solid was heated to 300 °C with a ramp rate of 1.5 °C/min
in a muffle furnace and maintained for 2 h. The resulting solid was then
Scheme 1. Schematic diagram for the hydrogenation of phthalates.
2
reduced in an H atmosphere at 450 °C for 2 h and the obtained catalyst
is denoted as Ni/MMT-DP.
stability, and strong electrostatic force with metal nanoclusters due to
its special structure [27]. Therefore, MMT has been applied in the
construction of novel nanocomposites for broad applications, such as
adsorption and catalysis [28]. However, there is no report the hydro-
genation of phthalates over MMT supported catalysts.
Preparation of Ni/MMT-B
3 2 2
In a typical run, 0.99 g of Ni (NO ) ·6H O was dissolved in 1.0 mL of
deionized water in a 50 mL beaker. Then, 1.0 g of MMT was added into
the above nitrate solution under stirring and dried at 80 °C overnight.
After that, 0.1 g of the dried precursor was dispersed in 10 mL of
In
a continuation of our research on nickel-based catalysts
deionized water. NaBH
mixed solution under stirring in an ice water bath. After standing for
min, the black precipitate was filtered and then washed with deio-
4
solution was then dropwise added into this
[
24,29,30], we prepared a series of MMT supported nickel-based cat-
alysts by different methods and applied them in the hydrogenation of
DOP, the most widely used phthalate plasticizer [1]. Notably, a catalyst
prepared by an ammonia evaporation method (Ni/MMT-AE) showed
excellent catalytic performance, which can be recycled ten times under
harsh reaction conditions, comparable to most of the noble metal cat-
alysts. To clarify the inherent reason between the structure and cata-
lytic performance of the Ni/MMT catalysts, the relationship between
preparation methods and performance was studied and clarified.
5
nized water to pH = 7–8, followed by three times of washing with
ethanol. The obtained catalyst is denoted as Ni/MMT-B.
Characterization of catalysts
X-ray powder diffraction patterns (XRD) were obtained on a D8
ADVANCE X-ray diffractometer using a Cu Kα radiation source.
Brunauer-Emmett-Teller (BET) surface area, pore volume and pore size
Experimental
2
distributions were obtained from the N adsorption/desorption iso-
therms at -196 °C using a Micromeritics Tristar II 3020 specific surface
and pore analyzer. The pore volume and pore size distributions were
calculated by the Barrett-Joyner-Halenda (BJH) method. Transmission
electron microscopy (TEM) was performed on a Jeol Jem-2100 F
Chemicals and reagents
All chemicals are analytical degree and used without further pur-
ifications. Montmorillonite was purchased from Aladdin Reagent
transmission electron microscope. H
2
-Temperature programmed re-
(
Shanghai) Co., Ltd. DOP, n-hexane and sodium hydroxide were pur-
duction (H -TPR) was carried out on a Micromeritics AutoChem II 2920
2
chased from Tianjin Kermel Chemical Reagent Factory. Nickel nitrate
hexahydrate was purchased from Sinopharm Group Chemical Reagent
Co., Ltd. Sodium borohydride was purchased from Fuchen Reagent Co.,
Ltd. Ammonia water and anhydrous ethanol were purchased from
Tianjin East China Reagent Factory. Ultrapure Ar (99.999 %) and 10 vol
instrument. X-ray photoelectron spectrometer (XPS) was collected on a
PHI 1600 spectrometer using a Mg Kα source.
Catalyst activity tests
%
2
H /Ar were purchased from Baoding Zhuoda Gas Co., Ltd.
DOP hydrogenation was performed in a 100 mL stainless-steel au-
toclave equipped with a mechanical stirrer and an electric heating
system. In a typical run, 2.7 g of DOP, 0.1 g of catalyst, and 60 mL of n-
hexane were added into the autoclave. The autoclave was filled with
Preparation of catalysts
H
2
, followed by evacuation, three times to exclude the residual air.
Pretreatment of support
Then, it was pressured to 5.0 MPa with H and heated to 150 °C. The
2
To remove water and other impurities adsorbed in the pores of
MMT, 10.0 g of MMT was heated to 450 °C with a heating rate of 2.5 °C/
min and maintained for 2 h.
hydrogenation reaction proceeded 1 h with a stirring speed of 500 rpm.
Subsequently, the reaction mixture was cooled to room temperature
and analyzed by an Agilent 7820 A gas chromatograph (GC). The
structure of products was confirmed by a Thermo Trace 1300 gas
chromatography and mass spectrometry (GC–MS).
Preparation of Ni/MMT-AE
3 2 2
In a typical run, 0.99 g of Ni (NO ) ·6H O was dissolved in 34 mL of
deionized water under stirring, followed by the addition of 1.0 g of
MMT. Then, 25 % aqueous ammonia was dropwise added to adjust the
pH value of the suspension to 11−12. Subsequently, the suspension
was stirred at 40 °C for 4 h and the temperature of oil bath was then
heated to 80 °C to evaporate ammonia until the pH of the suspension
dropped to 7. The obtained suspension was filtered and washed with
deionized water for several times, followed by three times of washing
with ethanol and then dried at 80 °C for 12 h. The obtained solid was
calcined at 200, 300, 400, and 500 °C for 2 h with the heating rate of
Results and discussion
Characterization of catalysts
The physicochemical properties of different Ni/MMT catalysts were
first evaluated and the results are shown in Table 1. Obviously, the Ni
content in the Ni/MMT-B catalyst (13.53 %) is much lower than those
of Ni/MMT-DP and Ni/MMT-AE (both 18.18 %), which can be ascribed
to the leaching of the active Ni species during preparation. Notably, the
Ni/MMT-AE catalyst showed the largest BET surface area, pore volume,
1
4
.5 °C/min, respectively. The resulting metal oxide was reduced at
50 °C for 2 h under H atmosphere (Scheme 2). The obtained catalysts
2
2
H -chemisorption value, metallic surface area and metal dispersion,
are denoted as Ni/MMT-AE-X (X represents the calcination tempera-
ture).
suggesting that the active nickel species of the Ni/MMT-AE catalyst
were highly dispersed on the MMT support. Furthermore, the
2

S. Nie, et al.
Molecular Catalysis 495 (2020) 111156
Scheme 2. Schematic diagram for the preparation of Ni/
MMT-AE.
physicochemical properties of the Ni/MMT-AE catalysts prepared by
different calcination temperatures (Table S1) showed that the catalyst
calcined at 300 °C displayed the largest hydrogen adsorption, metal
surface area and metal dispersion, although the catalyst calcined at
uneven shape with an average particle diameter of 5.1 nm, together
with certain aggregation (Fig. 3d). The Ni nanoparticles were also un-
evenly distributed in the Ni/MMT-B catalyst, which agglomerated to
bulk on the MMT support (Fig. 3e). The average particle diameter of Ni
nanoparticles in the Ni/MMT-B catalyst was 14.8 nm (Fig. 3f), much
larger than that of the Ni/MMT-AE catalyst.
2
−1
500 °C showed the largest BET surface area (90 m g ).
N
2
adsorption-desorption and pore size distributions of catalysts
prepared by different methods and calcination temperatures are
showed in Figs. 1 and S1. The results indicated that all catalysts ex-
hibited isotherm of type IV. There was a hysteresis loop in the relative
pressure region of 0.4–1.0, indicating that adsorption mainly occurred
in the mesoporous region. Moreover, the hysteresis loop in the iso-
therms (Fig. 1 a, c and Fig.S1 a, b, c, d) was H3 type, suggesting that the
pore structures in these catalysts were flat slit, cracks and wedge-
shaped structures composed of flake granular material [31]. These
structures conform to the natural structure of MMT and are benefit for
mass transfer during the hydrogenation process.
Fig. 4 shows the TEM images of the used catalysts. Notably, the Ni
nanoparticles in the Ni/MMT-AE catalyst still remained uniformly dis-
persed and the average particle diameter was kept to be 4.2 nm even
after 10 runs (Fig. 4b). In contrast, the Ni nanoparticles obviously ag-
glomerated with an average particle diameter of 22 nm in the Ni/MMT-
DP catalyst after 10 runs (Fig. 4d). The Ni nanoparticles also increased
to 18 nm in the Ni/MMT-B catalyst after 5 cycles (Fig. 4f). The above
results suggested that the Ni/MMT-AE catalyst had not only the uni-
formly dispersed and smallest, but also the most stable Ni nano-
particles, mainly attributed to the special ammonia evaporation pro-
cess, in which ammonia and Ni could form a uniformly dispersed and
stable complex during the preparation, thereby preventing the reaction
Fig. 2 shows the XRD patterns of the catalysts prepared by different
methods. As for the calcined samples (Fig. 2 a), the typical diffraction
peaks of MMT appeared at about 2θ = 6.7°, 21.1 °,22.3°, 35.7° and
−
of the tiny Ni particles with OH to form large Ni clusters [34].
61.8°, indicating that the MMT structure did not change after nickel
2
H -TPR profiles of the Ni/MMT-AE and Ni/MMT-DP catalysts are
loading and calcination. The weak and wide diffraction peak at
θ = 43.7° was attributed to NiO [29,32], demonstrating that the nickel
species have been uniformly distributed on the MMT support with small
particle sizes. The others peak of Ni/MMT-B was distributed to the
crystallization of metal salts. After the samples were reduced (Fig. 2 b),
the peaks of MMT were unchanged. A new diffraction peak appeared at
shown in Fig. 5. According to the previous report [35–38], the reduc-
tion peaks between 200–400 °C could be ascribed to the reduction of
free NiO with weak interaction between support. The reduction peaks
appearing in the temperature range of 400–650 °C can be ascribed to
the reduction of NiO that had strong interaction with support. Ob-
viously, the Ni/MMT-DP showed three reduction peaks at 228, 314 and
388 °C, respectively, indicating that the Ni species in this catalyst were
mainly from bulk NiO, which had weak interaction with support. As for
Ni/MMT-AE, there were three reduction peaks at 353, 438 and 633 °C,
respectively. The little peaks at 353 °C was ascribed to the reduction of
the bulk NiO. The peaks at 438 and 633 °C were ascribed to the re-
duction of NiO that had strong interaction with MMT. The larger
amounts of the latter kind of NiO would be helpful for protecting the Ni
species from aggregation and leaching during the reduction and reac-
tion process, and in turn improve the catalyst’s stability.
2
2
2
θ = 44.5°, together with the disappearance of the diffraction peak at
θ = 43.7°, indicated the reduction of NiO to Ni in the Ni/MMT-AE and
Ni/MMT-DP catalysts [29]. However, there was no diffraction peak
related to Ni could be detected in the spectrum of Ni/MMT-B. The
nickel species in this sample are suggested to be in an amorphous state
[
33].
Then, the effect of calcination temperatures was studied (Fig. S2).
The diffraction peak at 2θ = 11.3° was attributed to Ni (OH) in the
2
calcined Ni/MMT-AE-200 (Fig. S2 a), indicating that the nickel species
in the calcined Ni/MMT-AE-200 was mainly present in hydroxide state.
In contrast, the catalysts calcined at higher temperatures showed dif-
fraction peaks at about 2θ = 43.7°, which can be attributed to NiO.
Furthermore, typical diffraction peak of metallic Ni appeared at
XPS analysis is helpful to clarify the chemical states of metals and
the interaction between metal and support. Thus, XPS spectra of the Ni/
MMT-AE and Ni/MMT-DP catalysts were tested to further under-
standing these issues. As can be seen, there were two states of Ni 2 p3/2
spectra in both catalysts (Fig. 6). According to the literature [39,40],
the binding energies of Ni and NiO are about 852 and 855 eV in the Ni 2
2
θ = 44.5° in all reduced catalysts (Fig. S2 b). Notably, the catalyst
calcined at 300 °C had the smallest metallic Ni particle size among the
catalysts studied, indicating higher Ni dispersion in this catalyst and
accounting for its highest activity.
p
3/2 spectra, respectively. Thus, the peaks at 852.96 and 852.63 eV
were attributed to the metallic Ni on the surface of the MMT support
[41], and the peaks at 855.98 and 856.04 eV were ascribed to the NiO
species of the catalysts [42]. Some NiO were mainly due to the oxida-
tion of the catalyst surface during the sample transfer before the XPS
characterization [43,44]. It was obvious that the binding energy of
metallic Ni in Ni/MMT-AE was higher than that in Ni/MMT-DP,
TEM images of the fresh catalysts are exhibited in Fig. 3. Obviously,
the Ni nanoparticles in the Ni/MMT-AE catalyst were uniformly dis-
persed on the MMT support (Fig. 3a) and the particle size was in the
range of 1−10 nm with an average particle diameter of 4.1 nm
(
Fig. 3b). For the Ni/MMT-DP catalyst, the Ni nanoparticles showed
Table 1
Physicochemical properties of catalysts of different preparation methods.
Catalyst
Nia content (wt.%)
Surface area
Pore volume (nm)
H
2
-chemisorption (cm3 g−1
)
Metal surface area (m2 g −1
)
Metal dispersion (%)
2
−1
(
m
g
)
Ni/MMT-AE
Ni/MMT-DP
Ni/MMT-B
13.53
18.18
18.18
89
83
7
0.16
0.14
0.04
1.45
1.26
0.63
27.98
24.17
16.33
4.20
3.63
2.45
a: Based on ICP results.
3

S. Nie, et al.
Molecular Catalysis 495 (2020) 111156
2
Fig. 1. N adsorption–desorption isotherm and pore size distributions of catalysts: (a, b) Ni/MMT-AE, (c, d) Ni/MMT-DP, (e, f) Ni/MMT-B.
indicating the stronger interaction between the Ni species and the MMT
support in Ni/MMT-AE than in Ni/MMT-DP [45,46]. Combined with
the MMT support, which can effectively suppress the agglomeration
and loss of the active Ni spices during reaction, thereby improve the
stability of the Ni/MMT-AE catalyst.
2
the H -TPR results, we can demonstrate that the ammonia evaporation
method can enhance the interaction between the active Ni spices and
Fig. 2. XRD patterns of the calcined (a) and reduced (b) catalysts.
4

S. Nie, et al.
Molecular Catalysis 495 (2020) 111156
Fig. 3. TEM images and particle size distribution of the fresh catalysts: (a, b) Ni/MMT-AE, (c, d) Ni/MMT-DP, (e, f) Ni/MMT- B.
Catalytic performance
selected as the best calcination temperature.
Conclusions
Preparation methods and calcination temperature were proven to
play a crucial role on the catalytic performance of the Ni/MMT catalysts
in DOP hydrogenation. A Ni/MMT-AE catalyst showed excellent ac-
tivity and stability, which could be steadily recycled ten times under
harsh reaction conditions. Moreover, compared to the catalysts pre-
pared by the deposition precipitation and chemical reduction method,
The influence of preparation methods on the catalytic performance
of Ni/MMT catalysts was first examined (Table 2). The conversion of
DOP was only 59 % over the Ni/MMT-B catalyst prepared by a chemical
reduction method. In contrast, the conversions of DOP were both 99 %
over the Ni/MMT-DP catalyst prepared by a deposition-precipitation
method and the Ni/MMT-AE catalyst prepared by an ammonia eva-
poration method, demonstrating their excellent catalytic activity. Fur-
thermore, the selectivity for HEHHP were all 99 % for these catalysts.
Considering stability was an important feature for industrial cata-
lysts [47], the stabilities of these catalysts were then investigated
2
the Ni/MMT-AE catalyst had the largest BET surface area, H -chemi-
sorption value, metallic surface area and metal dispersion. XPS and TPR
results demonstrated that the Ni/MMT-AE catalyst had stronger inter-
action between the Ni species and the MMT support, which could
suppress the agglomeration and loss of the Ni species during the reac-
tion, accounting for its good stability. The advantages of simple pre-
paration method, low cost, excellent activity and good stability make
this catalyst a good candidate for industrial hydrogenations under harsh
reaction conditions.
(
Fig. 7). Obviously, the stability of the Ni/MMT-B catalyst was very
poor as the conversion of DOP sharply dropped to 10 % only after five
runs (Fig. 7a). Meanwhile, the stability of the Ni/MMT-DP catalyst was
still not good enough with the conversion of DOP dropping to around
6
0 % after ten runs (Fig. 7b). In contrast, the stability of the Ni/MMT-
AE catalyst was perfectly good and the conversion of DOP kept over 90
after ten runs (Fig. 7c), which was higher than all nickel-based cat-
%
alysts and also comparable to most of noble metal catalysts in phthalate
hydrogenation (Table S2). Moreover, the effect of calcination tem-
perature on the catalytic performance of the Ni/MMT-AE catalyst was
also tested (Fig. 7d). It was found that the catalyst calcined at 300 °C
showed the best stability among the catalysts studied. Thus, 300 °C was
CRediT authorship contribution statement
Shilin Nie: Methodology, Validation, Formal analysis,
Investigation, Writing - original draft, Writing - review & editing.
5

S. Nie, et al.
Molecular Catalysis 495 (2020) 111156
Fig. 4. TEM images and particle size distribution of used catalyst: (a, b) Ni/MMT-AE, (c, d) Ni/MMT-DP, (e, f) Ni/MMT-B.
Fig. 6. XPS of Ni 2 p3/2 spectra in Ni/MMT-AE (a) and Ni/MMT-DP (b) cata-
lysts.
2
Fig. 5. H -TPR profiles of the Ni/MMT-AE and Ni/MMT-DP catalysts.
6

S. Nie, et al.
Molecular Catalysis 495 (2020) 111156
Table 2
Catalytic performance of the Ni/MMT catalysts by prepared different methods.
Catalyst
DOP conversion (%)
DEHHP selectivity (%)
DEHHP yield (%)
Ni/MMT-B
Ni/MMT-DP
Ni/MMT-AE
59
99
99
99
99
99
58
98
98
Reaction conditions: 2.7 g DOP, 0.1 g catalyst, 60 mL n-hexane, 150 °C, 5.0 MPa H
2
, 500 rpm, 1 h.
Fig. 7. Stability of catalysts: (a) Ni/MMT-AE of different calcination temperatures, (b) Ni/MMT-AE-300, (c) Ni/MMT-DP, (d) Ni/MMT-B.
Conditions: 2.7 g DOP, 0.1 g catalyst, 60 mL n-hexane, 150 °C, 5.0 MPa H , 500 rpm, 1 h.
2
Huafan Li: Validation, Formal analysis, Investigation. Jingru Qin:
Validation, Formal analysis, Investigation. Yansu Wang: Methodology,
Supervision. Libo Niu: Methodology, Supervision. Ligong Chen:
Supervision. Guoyi Bai: Conceptualization, Methodology, Resources,
Acknowledgements
Financial support by the National Natural Science Foundation of
China (21676068) and the Natural Science Foundation of Hebei
Province (B2019201341) is gratefully acknowledged.
Writing
- review & editing, Supervision, Project administration,
Funding acquisition.
Appendix A. Supplementary data
Declaration of Competing Interest
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.mcat.2020.111156.
The authors report no declarations of interest.
7

S. Nie, et al.
Molecular Catalysis 495 (2020) 111156
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