Monodisperse nickel-nanoparticles for stereo- and chemoselective hydrogenation of alkynes to alkenes

Article abstract of DOI:10.1016/j.jcat.2018.12.018

Here, we report the use of monosaccharides for the preparation of novel nickel nanoparticles (NP), which constitute selective hydrogenation catalysts. For example, immobilization of fructose and Ni(OAc)₂ on silica and subsequent pyrolysis under inert atmosphere produced graphitic shells encapsulated Ni-NP with uniform size and distribution. Interestingly, fructose acts as structure controlling compound to generate specific graphitic layers and the formation of monodisperse NP. The resulting stable and reusable catalysts allow for stereo- and chemoselective semihydrogenation of functionalized and structurally diverse alkynes in high yields and selectivity.

Full text of DOI:10.1016/j.jcat.2018.12.018

Journal of Catalysis 370 (2019) 372–377
Contents lists available at ScienceDirect
Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat
Monodisperse nickel-nanoparticles for stereo- and chemoselective
hydrogenation of alkynes to alkenes
Kathiravan Murugesan a, Ahmad S. Alshammari b, Manzar Sohail a, Matthias Beller a,
,
⇑
Rajenahally V. Jagadeesh a,
⇑
a Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert Einstein-Str. 29a, 18059 Rostock, Germany
b King Abdulaziz City for Science and Technology, Riyadh 11442, Saudi Arabia
a r t i c l e i n f o
a b s t r a c t
Article history:
Here, we report the use of monosaccharides for the preparation of novel nickel nanoparticles (NP), which
constitute selective hydrogenation catalysts. For example, immobilization of fructose and Ni(OAc)2 on sil-
ica and subsequent pyrolysis under inert atmosphere produced graphitic shells encapsulated Ni-NP with
uniform size and distribution. Interestingly, fructose acts as structure controlling compound to generate
specific graphitic layers and the formation of monodisperse NP. The resulting stable and reusable cata-
lysts allow for stereo- and chemoselective semihydrogenation of functionalized and structurally diverse
alkynes in high yields and selectivity.
Received 3 September 2018
Revised 30 November 2018
Accepted 17 December 2018
Keywords:
Ni-nanoparticles
Monosaccharides
Hydrogenation
Alkynes
Ó 2019 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Alkenes
1. Introduction
stable Ni-nanoparticles with identical size (6 nm) and even distri-
bution are produced, which constitute reusable and highly selec-
The valorization of renewable resources for the production of
chemicals, materials, energy and life science molecules continues
to be an important goal of chemical research [1]. Among the feed-
stocks, simple monosaccharides such as glucose, fructose, galac-
tose and mannose serve as primary energy source in most of
organisms, from bacteria to humans [2]. In the past decade, some
of these sugars, especially fructose and glucose, became interesting
for the production of platform chemicals such as 5-
hydroxymethylfurfural (5-HMF), levulinic acid (LA), formic acid
(FA), acetic acid and furfural [1c,3]. Compared to synthetic
valorizations, the utilization of monosaccharides for the
preparation of nano-scale materials and catalysts is less explored
[1–4]. In general, a majority of such materials were prepared by
direct pyrolysis of biomass, which acted as self-sacrificing support,
along with metal salts [5,6]. However, achieving stable nanoparti-
cles with controlled size and uniform distribution still remains
challenging in these processes [4,5]. To overcome these limitations,
here we describe the preparation of monodisperse nickel nanopar-
ticles from monosaccharide-Ni acetate templates on silica and sub-
sequent pyrolysis. As a result, graphitic shells encapsulated highly
tive hydrogenation catalysts for the conversion of alkynes to
alkenes.
The hydrogenation of alkynes to alkenes is a versatile and envi-
ronmentally benign process applied in both research laboratories
and industries [6]. In the latter case, this transformation is used
to ‘‘purify” bulk alkenes, which serve as central intermediates in
the chemical and petrochemical industries [6a,7]. Noteworthy,
stereo selective access to either E- or Z-alkenes, which are found
to be the integral parts of numerous biologically active
compounds, is important in synthetic organic chemistry and drug
discovery [6a,8]. Regarding the catalysts for this transformation,
the so-called Lindlar catalyst (Pd/CaCO3 poisoned with Pb(OAc)2
and quinoline) constitutes an industrially used state-of-the-art-
system to produce Z-alkenes [9]. However, other precious metal
catalysts based on Ru [10a–10d], Pd [10e–10g] and Au [10h,10i]
have been also disclosed for the semihydrogenation of alkynes. In
addition to precious metal catalysts, in recent years Fe-[11a–
11d], Co-[11e–11g], Ni-[11h–11j], Cu-[11k] and V-[11l] based
both homogeneous [11a,11b,11f,11l] and heterogeneous[11c–
11e,11g–11j] catalysts have also been developed for this process.
Despite all these achievements, the development of practical
base-metal catalysts for chemo- and stereo-selective semi-
hydrogenation of structurally challenging alkynes is still desired.
⇑
Corresponding authors.
E-mail addresses: matthias.beller@catalysis.de (M. Beller), jagadeesh.jajenahally
@catalysis.de (R.V. Jagadeesh).
https://doi.org/10.1016/j.jcat.2018.12.018
0021-9517/Ó 2019 The Author(s). Published by Elsevier Inc.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

K. Murugesan et al. / Journal of Catalysis 370 (2019) 372–377
373
NMR data were recorded on a Bruker ARX 300 and Bruker ARX 400
2. Experimental section
spectrometers using DMSO d6, CD3OD and CDCl3 solvents.
2.1. Materials and methods
2.2. Preparation of Ni-fructose@SiO2 template and pyrolysis to obtain
nanomaterial
All substrates were obtained commercially from various chem-
ical companies and the purity has been checked before using.
Nickel(II) acetate tetrahydrate (cat no. 379883-10G), D-(À)-
Fructose (cat no F0127-500G), D-(+)-Glucose (cat no G8270-
100G), D-(+)-Mannose (cat no 3458-28-4), D-(+)-Galactose (cat
no G0750-10G) were purchased from Sigma-Aldrich Acetonitrile
(ACN, code- 149520010; 99%) was obtained from Across Chemi-
cals. Silica (Aerosil OX-50) was obtained from Evonik. The pyrolysis
experiments were carried out in Nytech-Qex oven.
The TEM measurements were performed at 200 kV with an
aberration-corrected JEM-ARM200F (JEOL, Corrector: CEOS). The
microscope is equipped with a JED-2300 (JEOL) energy-dispersive
x-ray-spectrometer (EDXS) and an Enfinum ER (GATAN) with Dual
EELS for chemical analysis. The aberration corrected STEM imaging
(High-Angle Annular Dark Field (HAADF) and Annular Bright Field
(ABF)) were performed under the following conditions. HAADF and
ABF both were done with a spot size of approximately 0.1 nm, a
convergence angle of 30–36° and collection semi-angles for HAADF
and ABF of 90–170 mrad and 11–22 mrad respectively. Dual EELS
was done at a CL of 4 cm, an illumination semi angle of 21.3 mrad
and an entrance aperture semi angle of 19.8 mrad. The solid sam-
ples were deposed without any pretreatment on a holey carbon
supported Cu-grid (mesh 300) and transferred to the microscope.
The average particle diameter and size distribution were calculated
using Java image tool software (ImageJ), based on the data of an
average of 100–200 particles. XRD powder patterns were recorded
on a Stoe STADI P diffractometer, equipped with a linear Position
In a 50 mL round bottomed flask, D-fructose (800.2 mg) in
20 mL distilled water (H2O) was stirred for 2–3 min at 100 °C and
then nickel (II) acetate tetrahydrate (381.57 mg) was added. Then,
the round bottomed flask containing reaction mixture was placed
into an aluminum block preheated at 100 °C and stirred for 20–
30 min by fixing reflux condenser Then, 1.2 g of silica (Aerosil-
OX-50) was added followed by the addition of 15 mL H2O and
the reaction mixture again was stirred at 100 °C for 4–5 h by fixing
reflux condenser. Then, the reflux condenser was removed and the
round bottomed flask containing reaction products were allowed
to stand without stirring and closing for 20 h at 100 °C in order
to slow evaporation of H2O. After the evaporation of solvent and
ensuring the complete drying, the material was cooled to room
temperature and grinded to fine powder. The powdered material
was pyrolyzed at the defined temperature (600 °C, 800 °C and
1000 °C) for 2 h under an argon atmosphere and then cooled to
room
temperature
after
pyrolysis.
Ni-materials
(Ni-
monosaccharide-SiO2-800) using other monosaccharides such as
glucose, mannose and galactose were also prepared using the same
procedure.
Elemental analysis of Ni-fructose@SiO2-800: Ni = 4.8 wt%,
Si = 34.41 wt%, C = 7.34 wt% and H = 0.05 wt%.
3. Results and discussion
Sensitive Detector (PSD) using Cu Ka radiation (k = 1.5406 Å). Pro-
cessing and assignment of the powder patterns was done using the
software WinXpow (Stoe) and the Powder Diffraction File (PDF)
database of the International Centre of Diffraction Data (ICDD).
X-ray photoelectron spectroscopy (XPS) analysis were carried out
in a PHl 5000 VersaProbe Scanning ESCA microprobe (ULVAC-
PHI, Japan/USA) instrument at a base pressure of 5.5 Â 10–7 Pa.
We started our investigations by the preparation of novel Ni-
nanoparticles (Ni-NP) using simple fructose and Ni-acetate as pre-
cursors. First, we created a Ni-fructose template on SiO2 by mixing
the components in water and refluxing them at 100 °C. After slow
evaporation of water and drying, the template was formed (Fig. 1).
Subsequently, this templated solid compound was pyrolyzed at
800 °C under argon atmosphere (Fig. 1). In addition to fructose,
Ni-NP was also prepared using other monosaccharides such as glu-
cose, galactose and mannose under similar conditions. Hereafter,
these Ni-materials are labelled as Ni-monosaccharide@SiO2-x,
where x defines the pyrolysis temperature.
All the prepared new materials were tested for the hydrogena-
tion of diphenylacetylene as benchmark reaction (Table 1). We
were surprised to find that all of the catalysts prepared using dif-
ferent monosaccharides showed excellent activity and selectivity
to produce > 94% of stilbene with selectivities of 99% for the Z-
isomer (Table 1; entries 1–4). Variation of the pyrolysis tempera-
ture between 600 and 1000 °C, revealed good activity for the mate-
rial pyrolyzed at 600 °C, while higher temperature resulted in a less
active catalyst (Table 1; entries 5–6). Pyrolysis of simple nickel
acetate on silica (Ni@SiO2-800) resulted in a significantly less
X-ray source of Al-K
a (hm = 1486.6 eV) with spot size of 200 mm
has been used. The analyzer of 187.850 eV was used with the
power of 25 W at pass energy 180 eV with a 0.4 eV energy step,
and the core-level spectra were acquired 10 at pass energy
58.70.5 eV with a 0.5 eV energy step. For quantitative analysis
the peaks were deconvoluted with Gaussian-Lorentzian curves
using CasaXPS software, the peak area was divided by a sensitivity
factor obtained from the element specific Scofield factor and the
transmission function of the spectrometer. N2 physisorption anal-
ysis at À196 °C was recorded using a Micromeritics ASAP 2020
analyzer. Prior to analysis, approximately 0.1–0.15 g of each cata-
lyst sample was outgassed for 4 h at 250 °C in an atmosphere of
N2. The total specific surface area, pore volume, and pore size were
analyzed by single or multi-point BET methods. CO chemisorption
experiments were performed by using a Micromeritics AutoChem
II 2920. Experiments were conducted at 30 °C by injecting 10%
CO/Ar into the reduced catalyst bed. Pulses were injected by means
of a calibrated sample loop (Vloop = 1 mL).
All catalytic experiments were carried out in 300 mL and
100 mL autoclaves (PARR Instrument Company). In order to avoid
unspecific reactions, all catalytic reactions were carried out either
in glass vials, which were placed inside the autoclave, or glass/
Teflon vessel fitted autoclaves. GC and GC-MS were recorded on
Agilent 6890N instrument.
GC conversion and yields were determined by GC-FID, HP6890
Fig. 1. Preparation of graphitic shells encapsulated Ni-nanoparticles supported on
silica by the pyrolysis of nickel acetate-fructose-SiO2 template.
with FID detector, column HP530 m  250 mm  0.25
lm.1H, 13C

374
K. Murugesan et al. / Journal of Catalysis 370 (2019) 372–377
Table 1
Hydrogenation of diphenylacetylene: Activity and selectivity of Ni-catalysts.a
Entry
Catalyst
Conv (%)
Yield of alkene (%)
Selectivity (Z:E)
Yield of alkane (%)
1
2
3
4
5
6
7
8
9
Ni-fructose@SiO2-800
Ni-glucose@SiO2-800
Ni-mannose@SiO2-800
Ni-galactose@SiO2-800
Ni- fructose@SiO2-600
Ni-fructose@SiO2-1000
Ni@SiO2-800
>99
>99
>99
>99
88
60
27
<2
<2
94
94
94
94
82
51
25
<1
<1
99:1
99:1
99:1
99:1
97:3
97:3
99:1
–
5
5
5
5
6
5
–
–
–
Ni + fructose@SiO2
Ni(OAC)2 + Fructose
–
Reaction conditions: 0.5 mmol of diphenylacetylene, 10 mg of catalyst (1.6 mol% Ni), 10 bar H2, 2 mL acetonitrile, 110 °C, 15 h, yields were determined by GC using n-
hexadecane standard.
active catalyst (Table 1; entry 7). Notably, all the non-pyrolyzed
catalysts are completely inactive (Table 1, entries 8–9).
In order to know the structural features as well as to understand
the activity and selectivity of these novel materials, detailed char-
acterization by HRTEM (high resolution transmission electron
microscopy), EDX (energy-dispersive X-ray spectroscopy), XRD
(X-ray powder diffraction) and XPS (X-ray photoelectron spec-
troscopy) were performed TEM analysis of the most active catalyst
(Ni-fructose@SiO2-800) revealed the formation of identical
monodisperse metallic Ni-nanoparticles with size of 6 nm
(Fig. 2a and Fig. 3). Interestingly all of these particles are sur-
rounded by 3–4 thin layers of graphitic shells (Fig. 2b). The HRTEM
image (Fig. 2c) displays the polycrystalline structure and its
selected lattice fringe has a distance of 0.18 nm. Fig. 2d shows
Fig. 3. EDX spectrum of Ni-fructose@ SiO2-800.
the selected area of electron diffraction (SAED) patterns. The
observed concentric rings indicate the formation of well-
crystallized Ni-particles. The deep rings noticed in the pattern cor-
responds to the reflection of the (1 1 1), (2 0 0), and (2 2 0) planes,
which is in line with the results obtained using XRD. Increasing the
pyrolysis temperature to 1000 °C, the catalyst becomes less active
(Ni-fructose@SiO2-1000). This material contains completely metal-
lic Ni, but in less quantity compared to Ni-fructose@SiO2-800
(Fig. 4). In addition, the nanoparticles are surrounded by thicker
(6–10 layers) graphitic shells (Fig. 4b). The less active material
(Ni(OAc)2@SiO2-800) prepared without D-fructose contains a mix-
ture of nickel oxide- (NiO) and metallic Ni-nanoparticles with
wider size distribution ranging between 5 and 35 nm (Fig. 5).
Fig. 4. TEM images of Ni-fructose@ SiO2-1000 material.
As observed in Fig. 5a, several nano-sized particles appeared to
be attached and agglomerate to form a flower-like shape. All of
these nanoparticles are not surrounded by graphitic shells. The dif-
ferent phases of Ni in both active and less active catalysts are also
confirmed by the XRD data (Fig. S1), which is in agreement to the
TEM analysis. Further, XPS analysis was carried out to elucidate the
chemical states of the elements. The survey scan of most active cat-
alyst (Ni-fructose@SiO2-800) showed the presence of Ni, C, O and Si
elements (Figs S3–S6). After deconvolution, the peaks present at BE
852.9 eV (Ni2p3/2) and BE 870.5 eV (Ni2p1/2) indicate the pres-
ence of metallic Ni near the surface (Fig. S2). In addition, the pres-
ence of a small quantity of Ni(II) is also evident by the peaks at BE
Fig. 2. TEM images of Ni-fructose@SiO2-800 catalyst. (a) = Monodisperse Ni-NP, (b)
= Ni-NP encapsulated within graphitic shells. (c) = Crystal planes of Ni-NP and (d)
= selected area electron diffraction (SAED) of Ni-NP.

K. Murugesan et al. / Journal of Catalysis 370 (2019) 372–377
375
Fig. 5. TEM images of Ni(OAc)2@SiO2 material.
855.1 eV (Ni2p3/2) and BE 874.9 eV (Ni2p1/2). The peak assigned
at BE 858.7 eV, which is of 5.8 eV higher than the Ni2p3/2 main
peak is due to surface and bulk plasmon loss of Ni(0) [12a]. The
high resolution XPS spectrum of C1s electrons were
deconvoluted into three peaks centered at BE 284.8, 286.1 and a
broad peak at 286.9 eV. These three, peaks can be assigned to
graphitic carbon C@C/CAC, CAO and C interacting with Ni atoms,
respectively (S4) [12a,12b]. The O1s spectrum shows the
presence of one type of O predominantly, which obviously stems
from SiO2 and is centered at 532.1 eV BE (Fig. S4) [12c]. Another
small peak centered at 534 eV could be assigned to CAO [12b].
The Si2p spectrum shows the presence of only one type of Si
(Fig. S5). The asymmetric shape of the Si2p peak is due to
overlapping of Si2p3/2 and Si2p1/2 [12c]. In the less active (Ni-
fructose@SiO2-1000) catalyst, only trace of Ni is present at the
surface (Fig. S2). Further to know the surface properties of the
catalysts, we conducted BET and chemisorption studies. As
shown in Table S1, the BET surface area of the catalyst increased
from 149.3 to 239.7 m2/g with increasing the pyrolysis
temperature from 800 to 1000 °C. The CO chemisorption studies
indicate that the metal dispersion is increased in case of Ni-
fructose@SiO2-800 (49.5%) compared to that of Ni-fructose@SiO2-
1000 (6.2%). All these characterization results evidence that the
most active catalyst (Ni-fructose@SiO2-800) is characterized by
the formation of defined metallic Ni-nanoparticles, which are
encapsulated within graphitic shells. Interestingly, fructose
generates graphitic layers and allows for the formation of
monodisperse Ni-nanoparticles.
After having successfully developed an active catalyst (Ni-
fructose@SiO2-800), we were interested in its general applicability
for the semi-hydrogenation of both internal and terminal alkynes.
As shown in Scheme 1, aromatic, heterocyclic and aliphatic inter-
nal alkynes were selectively hydrogenated to produce alkenes in
good to excellent yields. In all these cases high stereo-selectivity
with 98–100% for the Z-isomer formation was achieved
(Scheme 1).
In addition, the novel catalyst showed a high degree of chemos-
electivity. Different sensitive halogenated and functionalized alky-
nes were reduced to the corresponding olefins in up to 95% without
any significant dehalogenations (products 7–10). Remarkably, the
alkyne group was selectively semi-hydrogenated also in presence
of other reducible groups such as aldehyde, keto, nitrile and ester
(Scheme 1; products 11–12, 14–15). Thus, our Ni catalyst exhibits
both excellent regio- and chemoselectivity. In addition, propargylic
alkynes were reduced to produce allylic compounds in up to 87%
yields. Apart from aromatic substrates, aliphatic alkynes have also
been transformed to the corresponding alkenes in high yields and
Scheme 1. Ni-fructose@SiO2-800 catalyzed hydrogenation of internal alkynes to Z-
alkenesa. aReaction conditions: 1 mmol substrate, 30 mg catalyst (2.5 mol% Ni),
10 bar H2, 2 mL acetonitrile, 110 °C, 15 h, isolated yields. bZ: E isomeric ratios were
determined by NMR and GC-MS. c24 h. d2 mL dioxane solvent, e60 mg catalyst
(5 mol% Ni).
selectivities (Scheme 1; products 27–28). Next, the hydrogenation
of terminal alkynes was performed. Similar to internal alkynes,
here the CAC triple bond was selectively transformed to CAC dou-
ble bond in both aromatic and aliphatic compound (Scheme 2).
Furthermore, to showcase the generality and selectivity of our
novel Ni-based nano-catalyst, its reactivity was compared with
the Lindlar catalyst. For this purpose, the hydrogenation of 3

376
K. Murugesan et al. / Journal of Catalysis 370 (2019) 372–377
Scheme 3. Selective hydrogenation of phenylacetylene in the presence of styrene
using Ni-fructose@SiO2-800 showcasing the purification of alkenes. Reaction
conditions: 0.5 mmol phenylacetylene, 9.5 mmol styrene, 80 mg catalyst (0.6 mol
% Ni), 10 bar H2, 15 mL acetonitrile, 80 °C, 5 h.
100
90
80
70
60
50
40
30
20
10
0
1
2
3
4
5
6
7
Scheme 2. Semi-hydrogenation of terminal alkynes using Ni-fructose@SiO2-800
catalysta. aReaction conditions: 1 mmol substrate, 8 mg catalyst (0.6 mol% Ni),
10 bar H2, 2 mL acetonitrile, 110 °C, 5 h. Yields were determined by GC using n-
hexadecane as standard. bIsolated yields. b15 h. b15 mg catalyst (1.2 mol% Ni).
Fig. 6. Recycling of Ni-fructose@SiO2-800 for the hydrogenation of dipheny-
lacetylene to Z-stilbene. Reaction conations: 10 mmol diphenylacetylene 100 mg
catalyst (1.5 mol% Ni), 10 bar H2, 15 mL acetonitrile, 110 °C, 15 h, GC-yields, in all
the cases selectivity = 99:1 (Z: E).
selected functionalized alkynes (29–31) was carried out under
standard reaction conditions. As shown in Table 2, the Lindlar cat-
alyst showed no activity for the hydrogenation of 5-(phenylethy
nyl)nicotinonitrile (29) and the ester-substituted dipheny-
lacetylene (30). Although it exhibited excellent activity for the
hydrogenation of bis(4-bromophenyl)acetylene (31), significant
debromination occurred. Noteworthy, Ni-fructose@SiO2-800 suc-
cessfully worked for the semi-hydrogenation of all these
substrates.
Finally, the recycling and reusability of the optimal catalyst was
investigated. Indeed, Ni-fructose@SiO2-800 was highly stable
under the applied conditions and was successfully recycled and
reused up to 6 times without any significant loss of both activity
and selectivity (Fig. 6).
4. Conclusion
After having established the synthetic utility, selectivity and
generality of this novel Ni-catalyst, the practical applicability was
demonstrated by the hydrogenation of a small quantity of alkyne
in presence of excess of alkene.
As pointed out in the introduction, the removal of alkyne impu-
rities from alkenes is highly essential for the valorization of bulk
olefins. Using Ni-fructose@SiO2-800, 0.5 mmol of phenylacetylene
(32) was hydrogenated in presence of 9.5 mmol styrene (33) at
80 °C with 10 bar H2 (Scheme 3). Under these reaction conditions,
phenylacetylene was completely converted to produce 97% of styr-
ene and only 3% of ethylbenzene were obtained.
In conclusion, we demonstrate the use of inexpensive monosac-
charides for the controlled preparation of base metal nanoparticles
as sustainable selective hydrogenation catalysts. The immobiliza-
tion and pyrolysis of fructose and nickel acetate on silica produces
stable and reusable monodisperse Ni-nanoparticles encapsulated
in graphitic shells. These nanoparticles enable the hydrogenation
of a series of functionalized and structurally diverse aromatic,
heterocyclic and aliphatic alkynes to the corresponding alkenes
with excellent stereo- (98–100% Z-alkene formation) and chemo-
selectivity.
Table 2
Hydrogenation of selected substrates with Ni-fructose@SiO2-800 and Lindlar catalyst: Comparison of reactivity and selectivity.
Alkyne
Catalyst
Conv. (%)
Yied of alkene (%)
Selectivity (Z:E)
Ni-fructose @SiO2-800
Lindlar catalyst
>99%
<1
92%
<1
99:01
–
Ni-fructose @SiO2-800
Lindlar catalyst
>99%
<2
91%
<1
99:01
–
Ni-fructose @SiO2-800
Lindlar catalyst
>99%
>99
95%
65%
99:01
99:01
3Q% mono debrominated alkene
Reaction conditions: 1 mmol substrate, 2.5 mol% catalyst, 10 bar H2, 2 mL acetonitrile, 110 °C, 15 h.

K. Murugesan et al. / Journal of Catalysis 370 (2019) 372–377
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