Chemoselective Hydrogenation of Olefins Using a Nanostructured Nickel Catalyst

Article abstract of DOI:10.1002/zaac.202100124

The selective hydrogenation of functionalized olefins is of great importance in the chemical and pharmaceutical industry. Here, we report on a nanostructured nickel catalyst that enables the selective hydrogenation of purely aliphatic and functionalized olefins under mild conditions. The earth-abundant metal catalyst allows the selective hydrogenation of sterically protected olefins and further tolerates functional groups such as carbonyls, esters, ethers and nitriles. The characterization of our catalyst revealed the formation of surface oxidized metallic nickel nanoparticles stabilized by a N-doped carbon layer on the active carbon support.

Full text of DOI:10.1002/zaac.202100124

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.202100124
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Chemoselective Hydrogenation of Olefins Using a
Nanostructured Nickel Catalyst
Mara Klarner,[a] Sandra Bieger,[a] Markus Drechsler,[b] and Rhett Kempe*[a]
Dedicated to Prof. Dr. Josef Breu on the occasion of his 60th birthday.
The selective hydrogenation of functionalized olefins is of great
importance in the chemical and pharmaceutical industry. Here,
we report on a nanostructured nickel catalyst that enables the
selective hydrogenation of purely aliphatic and functionalized
olefins under mild conditions. The earth-abundant metal
catalyst allows the selective hydrogenation of sterically pro-
tected olefins and further tolerates functional groups such as
carbonyls, esters, ethers and nitriles. The characterization of our
catalyst revealed the formation of surface oxidized metallic
nickel nanoparticles stabilized by a N-doped carbon layer on
the active carbon support.
Introduction
3d metal catalysts step into the focus for many applications as
introduced by us[10] and the Beller group.[11] Also, the selective
olefin hydrogenation of α,β-unsaturated carbonyls, internal and
terminal unsaturated hydrocarbons was addressed with hetero-
geneous iron[12], cobalt[13] und nickel[14] catalysts. A highlight is
the work of Scharnagl et al.[13c], who were able to hydrogenate
terminal and internal alkenes with a high tolerance of functional
The selective hydrogenation of CÀ C double bonds is
a
challenging reaction and of high interest in academia and for
the production of industrially relevant chemicals.[1,2] More
specifically, the selective hydrogenation of olefins plays an
important role in the synthesis of vitamins such as biotin and β-
carotene.[3] Also drugs such as sertraline (anti-depressant),
betamethasone (glucocorticoid), and dihydroergotamine (anti-
migraine agent) are produced in this way.[4] The hydrogenation
of diisobutene to isooctane is important in the petrochemical
industry, because it is widely used as an anti-knock additive and
as a substitute for the previously used methyl tert-butyl ether.[5]
Furthermore, the olefin hydrogenation is used for the harden-
ing of natural oils in the food industry for better processing and
storage.[6] One possible route for olefin hydrogenation is
catalytic transfer hydrogenation,[7] which is usually accompanied
by the formation of easy-to-remove by-products. Most of the
known and industry-relevant catalyst systems are based on the
expensive noble metals ruthenium, rhodium, palladium, plati-
num and iridium or on difficult to handle and pyrophoric Raney
nickel.[8,9] In recent years, hydrogenation with nanostructured
°
groups using a Co@Chitosan catalyst (2.9 mol% Co) at 60 C and
°
4 MPa H2 pressure or at 150 C and 1 MPa H2, respectively.
Impressively, fatty acids and sunflower oil could also be
converted in high yields. Considering Ni catalysts, colloidally
stabilized Ni nanoparticles were used for the selective hydro-
genation of α,β-unsaturated carbonyl compounds at room
temperature and 4 MPa H2.[14f] In addition, supported systems
such as the Ni-phen@SiO2 catalyst (4 mol% Ni) were developed
to selectively convert substrates with different functional
[11e]
°
groups at 40 C, 1 MPa H2.
The application of flow-chemistry
techniques for the selective olefin hydrogenation with nickel is
particularly used in pharmaceutical manufacturing and in the
synthesis of valuable biobased building blocks.[15]
Here, we report on a nanostructured nickel catalyst, which
permits the selective hydrogenation of functionalized olefins.
This process is chemoselective and hydrogenation-sensitive
functional groups such as carbonyl compounds, esters, ethers
and nitriles are well tolerated. The Ni/C catalyst is easy-to-
synthesize in a two-step procedure starting from inexpensive
charcoal as support material. By controlled decomposition of a
Ni-salen complex precursor, catalytically active Ni nanoparticles
are generated and at the same time stabilized in a nitrogen-
doped carbon matrix on the support.[10d–g,11f]
[a] M. Klarner, S. Bieger, Prof. Dr. R. Kempe
Inorganic Chemistry II
University of Bayreuth
Universitätsstraße 30, 95440 Bayreuth (Germany)
E-mail: kempe@uni-bayreuth.de
[b] Dr. M. Drechsler
Bavarian Polymer Institute (BPI), KeyLab “Electron and Optical
Microscopy”
University of Bayreuth
Universitätsstraße 30, 95440 Bayreuth (Germany)
Supporting information for this article is available on the WWW
under https://doi.org/10.1002/zaac.202100124
Results and Discussion
The novel Ni/C catalyst was synthesized in a practical two-step
procedure according to the synthesis concept for 3d metal
catalysts developed by us[10d–g] (Figure 1): Firstly, the commer-
cially available carbon support (Norit CA1) was wet impreg-
nated with the novel Ni-salen(prop)(di-tert-butyl) complex in
© 2021 The Authors. Zeitschrift für anorganische und allgemeine
Chemie published by Wiley-VCH GmbH. This is an open access
article under the terms of the Creative Commons Attribution
License, which permits use, distribution and reproduction in any
medium, provided the original work is properly cited.
Z. Anorg. Allg. Chem. 2021, 647, 1–6
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Figure 1. Catalyst Synthesis and Characterization. (a) Synthesis of the Ni/C catalyst by (1) wet impregnation of commercial activated
charcoal (Norit CA1) with the Ni-salen(prop)(di-tert-butyl) complex (see Supporting Information for crystallographic data and complex
°
°
characterization), followed by (2) a pyrolysis step at 700 C in N2 flow and (3) a reduction step at 550 C in forming gas. (b, c) TEM analysis
verifies the homogenous distribution of Ni nanoparticles with a mean diameter of 19.5 nm. The size distribution of Ni particles is shown as
histogram. (d) XPS analysis of the Ni 2p3/2 region. The Ni0 nanoparticles are partially surface oxidized to Ni2+ species (about 17%). (e) XPS
analysis of the N 1s region. (f) Dark-field TEM analysis of the Ni/C catalyst. (g) Magnification by TEM exemplarily shows one Ni nanoparticle
of 23 nm in diameter surrounded by a 2–3 nm thick carbon layer (marked with white arrows).
tetrahydrofuran and the solvent was removed (see Supporting
Information for crystallographic data and complex character-
0.8 wt.% nitrogen from the decomposition of the Ni-salen
complex remained in the Ni/C composite. To date, it is unclear
to what extent the thickness and atomic composition of the N-
doped carbon layer plays a key role in the catalyst activity. It is
conceivable that the layer thickness and composition can be
influenced by the gas flow and the choice of salen precursor
during the catalyst preparation. We recorded XPS survey spectra
of the Ni/C catalyst in the range of 0–1200 eV (Supporting
Information, Figure S5) and observed expected lines for carbon,
nickel and traces of nitrogen. In the Ni 2p3/2 region (Figure 1d),
the combination of a metallic Ni0 signal at 852.6 eV and a
broader signal at about 854.6 eV, assigned to oxidized Ni2+, was
measured. The comparison of the intensity ratios at the dashed
positions showed that 83% Ni0 is present. Due to the handling
in air, the appearance of surface-oxidized metallic Ni nano-
particles is likely. The binding energy of the N 1s signal
observed is centered at 398.5 eV, possibly a remnant of the N-
containing precursor molecule and its decomposition products
(Figure 1e). We did not attempt to deconvolute the signal
because of the low intensity. The cubic phase of metallic Ni of
the freshly prepared catalyst could be indexed in the powder X-
ray diffraction pattern (Supporting Information, Figure S6). This
supports our thesis of surface oxidized Ni particles with metallic
core. Inductively coupled plasma optical emission spectroscopy
(ICP-OES) revealed a Ni content of 2.7 wt.%. This value deviates
from the targeted 4 wt.% because the amount of Ni deposited
on the support decreased due to the volatility of the Ni
precursor during the pyrolysis process (Supporting Information,
°
ization). This was followed by a pyrolysis step at 700 C in
°
nitrogen atmosphere and a reduction step at 550 C in forming
gas (90/10, N2/H2). We assume that the Ni catalyst is generated
by molecular dispersion of a defined volatile complex com-
pound on the support material during the pyrolysis step. The
subsequent tailored decomposition of the Ni-salen complex
leads to the formation of a N-doped carbon layer in which the
catalytically active Ni sites are embedded. Our catalyst is very
convenient to handle and remains catalytically active for several
months when stored in an inert atmosphere (Supporting
Information, Table S2). We performed transmission electron
microscopy (TEM) and X-ray photoelectron spectroscopy (XPS)
analysis to gain more insight into the catalyst structure. The
catalyst consists of homogeneously distributed, spherical Ni
nanoparticles with an average size of 19.5 nm and a fairly broad
size distribution (Figure 1b, c). An additional dark-field TEM
image verified the homogeneous distribution over the entire
carbon support (Figure 1f). Detailed analysis of one Ni particle
at the edge of an activated carbon platelet showed that the
nanoparticle is covered by a 2-3 nm thick carbon layer (Fig-
ure 1g). This layer could only be analyzed for exposed particles,
so that no average layer thickness could be determined for all
supported nickel particles. Referring to our last publication, we
claim that the decomposition of the Ni-salen complex leads to a
N-doped carbon matrix that stabilizes the Ni particles.[10d]
Elemental analysis of the catalyst material confirmed that
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Figure S2). Argon physisorption measurements demonstrated a
Isolated yields were determined for selected examples and are
26% decrease in the surface area of the bare carbon support
(929 m2/g) to 688 m2/g due to the catalyst generation process,
including the particle formation (Supporting Information, Fig-
ure S7). The DFT model (Ar at 87 K on carbon, cylindrical pores)
used to evaluate the pore size distribution showed an identical
bimodal pore distribution for the support material and for the
Ni/C catalyst. Both materials are predominantly microporous.
The catalyst synthesis does not affect the absolute pore size,
but only reduces the total pore volume.
given in parentheses.
Styrene (Table 1, 1a, 99%) and a total of 12 functionalized
styrene derivatives were selectively converted to the corre-
sponding ethylbenzene derivatives. Methyl-substituted com-
pounds were tolerated in para, meta and ortho position
(Table 1, 1b to 1d, 99–84%), as was the chloro-substituent
(Table 1, 1e–g, 78–60%) with ortho being the most challenging
position. Also, the hydrogenation of 4-bromostyrene was
realized in moderate yield (Table 1, 1h, 50%) without dehaloge-
nation. Electron-donating groups such as tert-butyl and meth-
oxy in para position (Table 1, 1i and 1j) were very well tolerated
by the Ni/C catalyst and the corresponding products were
obtained in quantitative yields. The double bond of the N-
heteroaromatic substrate 2-vinylpyridine, the 1,1-disubstituted
α-methoxy styrene and the polyaromatic 2-vinylnaphthalene
were hydrogenated in moderate to good yields, respectively
(Table 1, 1k to 1m). The hydrogenation of styrene at about
60% was chosen as the test reaction for a recyclability study.
The catalyst was used in five consecutive runs and showed no
reduction in activity in the first three (Supporting Information,
Figure S8). Then a minor decrease in activity was observed.
Next, we investigated the transformation of purely aliphatic
and aromatic unsaturated hydrocarbons. The conversion of
these non-functionalized olefins required harsher reaction
We investigated the Ni/C catalyst in the hydrogenation of
the CÀ C double bond of styrene as a catalytic benchmark test.
To our delight, a low catalyst loading (1.35 mol% Ni) and very
°
mild reaction conditions (0.2 MPa H2, 40 C) were necessary to
obtain ethylbenzene in
a
quantitative yield (Supporting
Information, Table S2, S3). A yield of 50% was still obtained at
room temperature and 0.1 MPa H2 pressure, highlighting the
catalytic activity of this base metal catalyst. In comparison with
commercial oxidic support materials (Al2O3, CeO2, SiO2, TiO2),
the combination of the Ni-salen precursor and the activated
carbon support was shown to be crucial for the high catalytic
activity. Remarkably, only the catalyst on silica support showed
moderate catalytic activity. No hydrogenation active Ni/C
catalyst could be prepared with nickel acetate as precursor,
highlighting the necessity of the Ni-salen complex (Supporting
Information, Table S2). Raney-Ni likewise led to quantitative
yield in this benchmark reaction. With the optimized reaction
conditions in hand, we were interested in the substrate scope.
All given product yields were determined by gas chromatog-
raphy (GC) and identified by GC-mass spectrometry (GC-MS).
°
conditions of 80 C and 1 MPa H2, whereas the catalyst loading
did not need to be increased (Supporting Information,
Table S4). 1,2-substituted CÀ C double bonds as in trans-stilbene
(Table 2, 2a, 99%) and internally cyclic olefins such as cyclo-
hexene, cyclooctene and norbornene were quantitatively con-
verted to the respective saturated compounds (Table 2, 2c to
2e). In addition, terminal double bonds in vinylcyclohexane,
octa-1,8-diene, 1-heptene, and 1-hexene (Table 2, 2b and 2f to
Table 1. Olefin hydrogenation with Ni/C: Investigation of styrene
derivatives.[a]
Table 2. Olefin hydrogenation with Ni/C: Investigation of unsatu-
rated hydrocarbons.[a]
R=4-Cl 1e, 78%
R=4-Me 1b, 99%
2-Cl
3-Cl
4-Br
1g, 60%
1f, 75%
1h, 50%
2-Me
3-Me
1d, 84%
1c, 99%
1a, 99% (98%)
1i, 99%
2a, 99% (90%)
2b, 99%
2c, 94%
1j, 99%
1k,[b] 58%
2d, 99% (99%)
2g, 99%
2e, 99%
2h, 99%
2f, 99%
2i, 91%
1l, 84%
1m, 43%
[a] 0.5 mmol substrate, 2.5 ml MeOH, 1.35 mol% Ni (14.7 mg Ni/C,
°
°
2.7 wt.% Ni), 40 C, 0.2 MPa H2, 20 h. [b] 80 C, 1 MPa H2. Yields
determined by GC using n-dodecane as an internal standard.
Products were analyzed by GC-MS. Isolated yields are given in
parentheses.
[a] 0.5 mmol substrate, 2.5 ml MeOH, 1.35 mol% Ni (14.7 mg Ni/C,
°
2.7 wt.% Ni), 80 C, 1 MPa H2, 20 h. Yields determined by GC using
n-dodecane as an internal standard. Products were analyzed by
GC-MS. Isolated yields are given in parentheses.
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Table 3. Olefin hydrogenation with Ni/C: Investigation of functional group tolerance.[a]
3a,[b] 92%
3b,[b] 99%
3c,[b] 99% (97%)
3d, 99%
3e, 99%
3f, 92%
3k, 84%
3p, 99%
3g, 99% (99%)
3l, 80%
3h, 99%
3m, 76%
3r, 68%
3i, 84% (80%)
3n, 78%
3j, 74%
3o, 99%
3q, 99%
3s,[b] 99%
°
[a] 0.5 mmol substrate, 2.5 ml H2O, 1.35 mol% Ni (14.7 mg Ni/C, 2.7 wt.% Ni), 80 C, 1 MPa H2, 20 h. [b] 2.5 ml MeOH. Yields determined by
GC using n-dodecane as an internal standard. Products were analyzed by GC-MS. Isolated yields are given in parentheses.
2h) were hydrogenated in 99% yield. Furthermore, it was
possible to convert a 1,1-disubstituted olefin to obtain the
product 3-methlyheptane in 91% (Table 2, 2i).
The application scope of the catalyst had been further
extended to the olefin hydrogenation in the presence of
hydrogenation-sensitive functional groups. Water was used as a
solvent for C=O functionalized substrates because the meth-
ylation of carbonyl functions by the solvent methanol occurred
as an undesirable side reaction. A total of 19 examples were
3p) and cinnamic acid ethyl ester (Table 3, 3q) were quantita-
tively converted to the respective saturated compounds. For
unknown reasons, only a moderate yield of 68% of ethyl
acetate (Table 3, 3r) could be obtained. In addition to the
numerous examples of oxygen-containing functional groups,
the C�N triple bond of an aliphatic nitrile was tolerated
(Table 3, 3s, 99%).
One reaction was performed with 20 times the amount of
substrate (10 mmol) to demonstrate the applicability of the
Ni/C catalyst on a larger scale. Styrene (95%) was converted to
the corresponding saturated product with slightly reduced
activity referred to the 0.5 mmol reaction.
°
selectively converted at 80 C and 1 MPa H2 pressure. Alcohol-
modified substrates (Table 3, 3a to 3c, 92–99%) did not
negatively affect the catalytic hydrogenation of CÀ C double
bonds by Ni/C. Likewise, N-vinyl derivatives of caprolactam and
pyrrolidone were quantitatively converted (Table 3, 3d and 3e)
without attacking the cyclic amide. Our Ni/C catalyst enables Conclusions
the challenging hydrogenation of olefins in the presence of α,β-
unsaturated ketones in very good yields. Internal cyclic carbonyl
compounds were converted more efficiently (Table 3, 3f to 3h,
92–99%) than non-cyclic ones (Table 3, 3i and 3j, 84% and
74%).
Furthermore, isolated mono- or trisubstituted CÀ C double
bonds were selectively hydrogenated in the presence of keto
groups (Table 3, 3k and 3l). Remarkably, hydrogenation-
In summary, we have developed a nickel catalyst that
selectively hydrogenates olefins under mild reaction conditions.
The Ni/C catalyst showed a high tolerance to hydrogenation-
sensitive functional groups such as carbonyl, ether, ester, and
nitrile.
sensitive α,β-unsaturated aldehydes were well tolerated. Not Acknowledgements
only a 1,2-di-substituted olefin (Table 3, 3m, 76%) but also the
challenging 1,2-tetrasubstituted 2-methyl-3-phenylbutenal (Ta-
ble 3, 3n, 78%) was selectively hydrogenated in good yields.
Only a minor trace of alcohol was observed as a byproduct.
Also, an aromatic and an aliphatic allyl ether (Table 3, 3o and
This work was supported by the German Research Foundation
(DFG SFB 840, B1). We thank R. Fertig for XRD, K. Ament for
PXRD and F. Baier for XPS analysis. Furthermore, we thank the
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access funding enabled and organized by Projekt DEAL.
Keywords: nickel catalyst · olefins · selective hydrogenation ·
sustainable catalysis
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Manuscript received: April 9, 2021
Revised manuscript received: May 4, 2021
Accepted manuscript online: May 5, 2021
Z. Anorg. Allg. Chem. 2021, 1–6
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ARTICLE
M. Klarner, S. Bieger, Dr. M.
Drechsler, Prof. Dr. R. Kempe*
1 – 6
Chemoselective Hydrogenation of
Olefins Using a Nanostructured
Nickel Catalyst