Ambient Hydrogenation and Deuteration of Alkenes Using a Nanostructured Ni-Core–Shell Catalyst

Article abstract of DOI:10.1002/anie.202105492

A general protocol for the selective hydrogenation and deuteration of a variety of alkenes is presented. Key to success for these reactions is the use of a specific nickel-graphitic shell-based core–shell-structured catalyst, which is conveniently prepared by impregnation and subsequent calcination of nickel nitrate on carbon at 450 °C under argon. Applying this nanostructured catalyst, both terminal and internal alkenes, which are of industrial and commercial importance, were selectively hydrogenated and deuterated at ambient conditions (room temperature, using 1 bar hydrogen or 1 bar deuterium), giving access to the corresponding alkanes and deuterium-labeled alkanes in good to excellent yields. The synthetic utility and practicability of this Ni-based hydrogenation protocol is demonstrated by gram-scale reactions as well as efficient catalyst recycling experiments.

Full text of DOI:10.1002/anie.202105492

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Ambient hydrogenation and deuteration of alkenes using a nano-
structured Ni-core-shell catalyst
Authors: Jie Gao, Rui MA, Lu Feng, Yuefeng Liu, Ralf Jackstell,
Rajenahally Jagadeesh, and Matthias Beller
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202105492
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10.1002/anie.202105492
Angewandte Chemie International Edition
RESEARCH ARTICLE
Ambient hydrogenation and deuteration of alkenes
using a nano-structured Ni-core-shell catalyst
Dedicated in memoriam to Professor Paul C. J. Kamer.
Jie Gaoa, Rui Maa, Lu Fengb, Yuefeng Liub, Ralf Jackstella, Rajenahally V. Jagadeesha*, Matthias
Bellera*
[a]
[b]
J. Gao, R. Ma, Dr. R. Jackstell, Dr. R. V. Jagadeesh and Prof.Dr. M. Beller
Leibniz Leibniz-Institut für Katalyse e.V.
Albert-Einstein-Str. 29a, D-18059Rostock, Germany
*Corresponding Authors: E-Mails: jagadeesh.rajenahally@catalysis.de ; matthias.beller@catalysis.de
L. Feng, Dr. Y. Liu
Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics, Chinese Academy of Science
457 ZhongshanRoad, 116023 Dalian, China
Abstract: A general protocol for the selective hydrogenation and
deuteration of a variety of alkenes is presented. Key to success for
these reactions is the use of a specific nickel-graphitic shell-based
core-shell structured catalyst, which is conveniently prepared by
impregnation and subsequent calcination of nickel nitrate on carbon
nickel® or the palladium-based Lindlar catalyst. Unfortunately,
both materialshave certain disadvantages: While the former one
is highlysensitive and requiresspecialhandling, the latter isquite
expensive. In addition, the majorityof these reactions require high
pressure of hydrogen (up to 50 bar) and sometimes higher
o
at 450 C under argon. Applying this nano-structured catalyst, both
reaction temperatures (>100 ℃), which requires specific
17
terminal and internal alkenes, which are of industrial and commercial
importance, were selectively hydrogenated and deuterated at ambient
conditions (room temperature using 1 bar hydrogen or 1 bar
deuterium), giving access to the corresponding alkanes and
deuterium-labelled alkanes in good to excellent yields. The synthetic
utility and practicability of this Ni-based hydrogenation protocol is
demonstrated by gram-scale reactions as well as efficient catalyst
recycling experiments.
equipment and additional energy.11,
In this respect, the
development of more active catalysts which allow for minimal
energy consumption and low pressure is highly desired, but
scientifically very challenging. So far, such hydrogenations can
be only achieved under mild conditions in the presence of
preciousmetal catalysts. However, at this point it should be also
noted that due to the exothermicity of hydrogenations for large
scale applications low temperature reactions are not ideal
because such processes would require cooling. Thus,
hydrogenations at ambient conditions offer specifically
advantages for fine chemical products and organic synthesis.
Apart from that, a modern state-of-the-art catalyst for olefin
hydrogenation should be based on 3d-metals due to their
availabilityand price advantages.
Introduction
Alkenes serve as key feedstocksand central intermediates
in chemical, pharmaceutical, petrochemical, and material
industries. Indeed, a varietyof bulkand fine chemicalsas well as
renewables contain C=C double bonds. Although the majority of
these products are used for further alkene polymerization1 or
functionalizations to give ketones,2 alcohols,3epoxides,4 amines,5
the apparently simple hydrogenation to give alkanes is also
important.6-11 Specifically, in the petrochemical industry
hydrotreating of petroleum and itsderivatives are applied on large
scale.12 Anotherprominentindustrial process isthe conversion of
di-isobutene mixture to iso-octane (2,4,4-trimethylpentane), an
important component of gasoline, commonlyused to increase the
knock resistance offuels. In addition, the selective hydrogenation
of bio-feedstockssuch as 2-methoxy-4-allylphenol (eugenol), (+)-
limonene and related terpenes is gaining increasing attention to
produce renewable finechemicals, e.g. fragrances.13-14
Notably, in recent years important breakthroughs were
reported for the hydrogenation of alkenes in the presence of
18-19
homogeneous Fe-, Co- and Ni-based complexes.6,
example, bis(NHSi) Ni
complexes,19 and iron
For
complexes,6 cobalt dihydrogen
dinitrogen complexes18 can be
successfully applied under mild conditions. However, these
homogeneous complexes are rather sensitive and/or require
sophisticated syntheticallydemanding ligands, which makesthem
less feasible for practicalhydrogenationsof alkenes. On the other
hand, heterogeneous catalysts are generally more stable and
permit easier recycling and reusability.20-28 In this respect, we
recently introduced nano-structured materials based on the
pyrolysisof cobalt saltsand biopolymers forthe hydrogenation of
alkenes, however these materials also showed no hydrogenation
reactivity at ambient conditions.11, 17 In fact, to the best of our
knowledge, until now 3d-metalbased heterogeneouscatalystsfor
the hydrogenation of alkenes at ambient conditions (1 bar
hydrogen, RT) were not reported, yet.
With respect to fine chemicals, catalytichydrogenations are
used in the synthesis of vitamins such as biotin, a vitamin K3
derivative, and -carotene. Moreover, olefin hydrogenation
processes are applied for the conversion of natural unsaturated
oils to processable and storable fats on multi-million-tonscalesfor
the food industries.15-16 Typically, these reductionsrelyon Raney
Here, we report the preparation of novelcore-shell Ni-nano
particles supported on Vulcan XC72R by impregnation and
subsequent calcination. The resulting materials exhibit excellent
1
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10.1002/anie.202105492
Angewandte Chemie International Edition
RESEARCH ARTICLE
activityforthe selective hydrogenation and deuteration of terminal
and internalalkenesincluding functionalized onesunderverymild
conditions.
To understand the effect of calcination temperature, Ni@C
was calcined at different temperatures (350-750 C). Among
o
these, only Ni@C-450 and Ni@C-550 were found to be active
(Table 1, entries 5-8). In addition, the influence of supports was
also evaluated. For this purpose, Ni-nitrate was impregnated on
Al2O3, V2O5, CeO2, TiO2, and C3N4and calcinated at 450 oC under
argon. However, all these materials were completely inactive
(Table S1). Next, the performance of Ni@C-450 in other solvents
such as toluene, acetonitrile, ether, tetrahydrofuran, and
isopropanolwasassessed (Table S2). Compared to methanol,all
other solvents showed poor catalyst activity. As a control
experiment, the reaction in theabsence of hydrogen revealed no
conversion of alkene, which confirms H2 as the sole reducing
agent and no transfer hydrogenation mechanism (Table S2).
Results and Discussion
Catalyst preparation and initial testing
To prepare highly active supported 3d-metal nanoparticles
for olefin hydrogenation, several metal nitrates(Fe, Mn, Co orNi)
were impregnated in MeOH on carbon (Vulcan XC72R), Al2O3,
V2O5, CeO2, TiO2, and C3N4. Upon slow evaporationof the solvent
the corresponding metal nitrates were adsorbed on to the support.
The resulting materials were calcined under argon at defined
temperatures (350-750 oC) to obtain a small library of potential
catalysts (Figure 1). Hereafter, we represent these supported
nanoparticlesas M@support-X, where M and Xdenotesthemetal
and pyrolysistemperature, respectively.
Characterizations of the Ni-based catalysts
To understand the structural features and reason for the
excellent activityof the specific Ni@C-450 catalyst, we performed
detailed characterization of this material and compared it with
other less active (Ni@C-550) and inactive materials (Ni@C-350
and Ni@Al2O3-450). X-ray diffraction(XRD) spectroscopyof the
most active (Ni@C-450) and less active (Ni@C-550) catalysts
revealed the presence of mainly metallic Ni particles, evidenced
by three diffractionpeaksat 44.5°, 51.8°and 76.4°(Figure 2a and
Figure 3a).28-29 In the inactive catalysts, Ni@C-350 and
Ni@Al2O3-450, the presence of mainly Ni-oxide (NiO) particles
are observed with the diffraction peaks at 37.2°, 43.3° and 62.9°
(FiguresS1 and S2).28-29 TEM analysisof most active (Ni@C-450)
and less active (Ni@C-550) catalysts (Figure 2c and Figure 3c),
confirmed the formation of uniformly distributed metallic Ni-
nanoparticleswith an average diameter of 8.60 nm and 11.06 nm,
respectively. Interestingly, Ni-nanoparticles in both these
materials are surrounded by graphitic shells, which resultsin the
formation of Ni NPs/graphitic shell-based core/shell structures
(Figures2d and Figure 3d). The formation of these newlyformed
graphitic shells is due to the carbonization of carbon support.30
The bigger particle size in Ni@C-550 (11.06 nm) catalyst
compared to Ni@C-450 (8.60 nm) is induced by the relatively
higher calcination temperature. To knowmore about the nature of
Ni-particleson the surface, XPSanalysiswas conducted. The Ni
2p spectra of four catalysts (Ni@C-450, Ni@C-350, Ni@C-550
and Ni@Al2O3-450)were deconvoluted into three contributionsat
~852.5 eV, ~853.8 eV and ~855.5 eVin the Ni2p3/2 region,which
are assigned to metallic nickel, NiO, and Ni2O3 respectively.29
These data revealed only the presence of Ni-oxide particles in
Ni@C-450 (Figure 2b), Ni@C-350 (Figure S4) and Ni@Al2O3-450
(Figure S5), while Ni@C-550 (Figure 3b) contained a mixture of
Ni-oxide and metallic Ni.
Figure 1. General preparation ofsupported 3d metal-based catalysts.
Initial catalytic experiments were carried out for the
hydrogenation of 1-decene as a benchmark reaction under
challenging reaction conditions (room temperature and 1 bar
hydrogen in methanol). As expected, all homogeneous metal
salts and their supported congeners were completely inactive
under these reaction conditions (Table S1). Next, we tested
calcinated materials, e.g., Fe@C-450, Cu@C-450, Co@C-450,
and Ni@C-450. None of the Fe-, Cu- and Co-based materials
showed any activity (Table 1, entries 1-3), instead the Ni-based
catalyst (Ni@C-450) exhibited excellent activity and 1-decene
was reduced to n-decane in quantitative yield (Table 1, entry4).
Table 1. Hydrogenation of 1-decene using different catalysts under ambient
conditions.
The structuraldefectsof Ni@C-350, Ni@C-450and Ni@C-
550 were analyzed using Raman spectroscopy (Figure S7). The
D and G band peaks at around 1354 and 1599 cm-1 were
observed in all these samples. The D band originated from the
defected carbon and the G band is due to crystallized graphitic
sp2 carbon.31-32 The differentintensityratios of D/G(ID/IG) resulted
from the calcination temperatures, which affect the interaction
between Ni and carbon support. Asshown in Figure S7, thedefect
degree of Ni@C-450 is the highest (ID/IG=1.003). As the
calcination temperature rise to 550 ℃, the value of ID/IG decreases
from 1.003 to 0.992, indicating that highercalcination temperature
increasesthe graphitization degree of thegraphite layer covering
Reaction conditions, 0.5 mmol 1-decene, 1 bar H2, 2 ml methanol, room
temperature (25-27 oC), 8 h. 20 mg heterogeneous catalyst (8 mol% Ni).
Conversion/yieldsweredetermined byGC using n-hexadecane as standard.
2
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10.1002/anie.202105492
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RESEARCH ARTICLE
nickel nanoparticles. This means the nickel nanoparticles in
Ni@C-550 were more tightly wrapped by the graphitic carbon
layers, which obviouslyhinderthe contact between reactantsand
nickel nanoparticles, consequently its catalytic activity is much
lower than that of the Ni@C-450 (Table 1, entries 12 and 14).
Finally, N2physisorption experimentswere conducted to study the
textural propertiesof the materials(Table S3, and FiguresS8-S9).
As shown in Table S3, Ni@C-450 has the largest specific
surface area of 204 m2/g; so it can provide more sites to adsorb
reactants. The recycled Ni@C-450 catalyst was also analyzed by
XRD, XPS and BET. XPSshowed the presence of metallic nickel
particles in this sample in addition to Ni-oxide particles. This is
attributable to the reduction of someof Ni-oxidesto metallicNi on
the surface of thecatalyst by hydrogen during the reaction (Figure
S6). However, no significant changes for the recycled catalyst
were observed compared to the fresh one by XRD (Figure S3)
and BET (FiguresS8 and S9).
All these characterization resultsrevealed that theformation
of monodisperse small Ni-nanoparticles and the generation of
graphiticshells, which surroundsthe particles are key features for
the most active catalytic material(Ni@C-450). The larger surface
area and higher degree of defects of Ni@C-450 catalyst can
provide more reactive sitesfor adsorption and catalysis. The core-
shell structure prevents metal leaching, which certainly improves
stability. Due to these structural features, Ni@C-450 showed the
best catalyticperformance forthe benchmark hydrogenation.
Hydrogenation of aliphatic olefins
The generalapplicability of Ni@C-450was first tested in the
hydrogenation of a series of aliphatic alkenes. Using the optimal
Ni-catalyst, simple alkenes including terminal acyclic (1-4) and
internal cyclic (5-10) were hydrogenated to give the
corresponding alkanes in excellent yields (Scheme 1). By
prolonging the reaction time, high conversion of more sterically
hindered internalcyclicalkenes (10-11) was achieved, too.
Scheme 1. Hydrogenation of aliphatic alkenesusing Ni@C-450 catalysta.
Figure 2. (a) XRD pattern, (b) Ni2p XPS spectra, (c) TEM images, and (d)
HRTEM images of Ni@C-450 catalyst. The insetof (c) showsthe particle were
uniformly distributed on the carbon support with an average diameter of 8.60
nm. The formation of Ni NPs/graphitic shell-based core/shell structures is
presented in (d).
Reaction conditions: a 0.5 mmol alkene, 20 mg catalyst (8 mol% Ni) 2 mL
methanol, RT, 1 bar H2, 8 h; b16 h. ⊥Yield were determined by GC using
hexadecane as standard. #Yieldsweredetermined by 1H NMR using mesitylene
as internal standard. Isolated yields.
Figure 3. (a) XRD spectra, (b) Ni2p XPS spectra, (c) TEM images, and (d)
HRTEM images of Ni@C-550 catalyst. The insetof (c) showsthe particle were
uniformly distributed on the carbon support with an average diameter of 11.06
nm. The formation of Ni NPs /graphitic shell-based core/shell structures is
presented in (d).
Alkenes containing hydroxyl and ether groups (14-16) are also
selectively hydrogenated. 2-Methoxy-4-allylphenol (18),
renewable feedstock derived from lignin, provided 2-methoxy-4-
propylphenol which is of potential interest for polymers33 and
a
3
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10.1002/anie.202105492
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RESEARCH ARTICLE
carbamates34 in 97% yield. Similarly, the more demanding 1,3,5- reducible groupssuch as aldehyde (47), ester (48), and ketones
tribromo-2-prop-2-enoxybenzene (19) was hydrogenated to
1,3,5-tribromo-2-propoxybenzene in excellent yield without any
reductive dehalogenation side reactions. Notably, functional
groups, such as nitrile, ketone, ester, and epoxide groups were
well tolerated during the hydrogenation process, too (21-27).
Finally, the natural monocyclic terpene (+)-limonene (28) was
selectively reduced to (+)-carvomenthene by using our catalytic
system.
(49).
Hydrogenation of sterically hindered alkenes, 1,n-dienes,
and trienes
As shown in Table 2, diverse internaland stericallyhindered
alkenes can be selectively hydrogenated in good to excellent
yieldsat comparably low temperature (45 °C). Both electron-rich
and electron-poor double bonds can be hydrogenated in high
yields under these conditions (compare entries 1, 3 and 7). In
case of (natural) substrates with more than one olefinic unit, in
generalcomplete hydrogenation can be achieved (entries 2, 4, 5,
6, and 9).
Hydrogenation of aromatic alkenes
Under the previously optimized conditions, a variety of
aromatic alkenes are selectively reduced, too. Styrene (29) and
substituted derivatives bearing electron-withdrawing (30-32) and
-donating groups (33-34) provided the corresponding ethyl
benzenes in quantitative yields. Hydrogenation of trans-stilbene
(37) was achieved in 98% yield. In addition, thehydrogenation of
1,1-disubstituted alkenes (39-42), which is challenging for many
catalysts7, 35-36 proceeded smoothly.
Table 2. Hydrogenation of sterically hindered alkenes, 1,n-dienes, and trienes
using Ni@C-450 catalyst.
Scheme 2. Ni@C-450 catalyzed hydrogenation of aromatic alkenesa.
Reaction conditions:20 mg Ni@C-450, 0.5 mmol substrate, 2 ml methanol, 16
h. a RT, 1 bar H2. b45 ℃, 5 bar H2. Yields were determined byGC.
Hydrogenation of sunfloweroil
The hydrogenation of vegetable oil is an important industrial
process to produce triglycerides with higher boiling point and
increased degree of saturation.11 To showcase the applicabilityof
the new catalyst, commercial sunflower oil consisting
predominantly of unsaturated fatty acid triglycerides(89% purity)
was hydrogenated at 25 bar for 18 h (Scheme 3).
Reaction conditions: a0.5 mmol substrate, 20 mg catalyst (8 mol% Ni) 2 mL
methanol, RT, 1 bar H2, 8 h; b16 h. ⊥Yields were determined by GC using
hexadecane as internal standard. #Yields were determined by 1H NMR using
mesitylene asinternal standard. Isolated yields.
As an example, 2-methyl-2,4-diphenylpentane was
obtained in 82% yield despite the steric hindrance of the two
phenyl groups (41). In several cases the hydrogenation of N-
heterocycles and amino-olefins is hampered by strong
coordination of thenitrogen atom(s), which hinders or slows down
C-C double bound reductions. Interestingly, with the present
catalyst olefinic bonds in presence of these N-moieties (43-44)
were reduced easily to give the corresponding alkanes in up to
85% yield. In addition to alkenes, aromatic alkynes can be
completely hydrogenated. Here, both terminal and internal
alkynessuch as phenylacetylene (45) and 1,2-diphenylacetylene
(46) were fully reduced to corresponding alkanes in 98% yield.
From a syntheticperspective it is interesting that Ni@C-450 also
allowed for the highlyselective hydrogenation of terminal(47) and
internal (48-50) C-C double bonds in the presence of other
Scheme 3. Hydrogenation ofsunflower oil over Ni@C-450 catalyst.
Reaction conditions: 2 ml sunflower oil, 20 mgNi@C-450 catalyst, 110 ℃, 18 h,
25 bar H2. Yield was calculated from the mass difference before and after
reaction. Details ofseparation is presented in the supporting information.
4
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RESEARCH ARTICLE
Notably, in these cases no additional solvent was used. Indeed,
hydrogenation took place already at 80 °C (48% conversion);
however increased conversion was obtained at 110 °C.
Afterwards, the reaction mixture was completely solidified. The
catalyst can be easily recycled from this solid mixture by
dissolving the crudeproduct in methanol and afterfiltration a white
solid is obtained, in which 58% of the olefinic groups were
hydrogenated.
presence of molecular hydrogen. In agreement with the result
from reaction 1, in the presence of MeOH-d4 no deuterium-
labeled product is formed (Scheme 4, reaction 3). Notably, in
deuteration studies with D2 (Table 3 and Scheme 4, reaction 4)
apart from the deuterated alkane, MeODwas also detected by 2H
NMR after the reaction. We presume MeOD is formed by H/D-
exchange between methanol and Ni-D species. Based on all
these results, we propose the following plausible reaction
mechanism: As shown in Scheme 5, initially H2 or D2 is activated
by the Ni@C-450 catalyst at room temperature, thereby leading
to the formation of active Ni-H or -D species. Based on the
formation of MeOD, we assume a reversible exchange between
Selective deuteration of alkenes
The performance of our Ni-based catalyst in the
hydrogenation of alkenes prompted us to test its the applicability
also for the deuteration of alkenesusing D2 gas. Such deuterium- Ni-H/D and MeO-H on the catalyst surface. After adsorption on
labeled compounds are useful probes in many mechanistic
investigations, including reaction kineticsas well as formetabolic
studies.18, 37-39 Gratifyingly, in presence of 1 bar of D2 at room
temperature seven alkenes were selectively converted into their
corresponding labeled alkaneswith excellent yields. As far as we
know, this isthe first example forachieving deuteration of alkenes
at ambient conditions using a heterogeneous non-noble metal
catalyst. Interestingly, in all cases the deuterium incorporation is
higher at the terminal position (α) compared to the internal
position (β), which has been also observed in mechanistic
experiments of a recently disclosed iron-catalyzed transfer
hydrogenation of olefins (for further mechanistic explanations,
see the next section).18
the surface of Ni@C-450, the alkene willinsert into the metal-H or
-D bond to provide the corresponding metal alkyl species. Since
deuterium incorporation is higher at the terminal position (α)
compared to the internal position (β) is observed after reaction,
we conclude a stepwise process for the formation of the new C-
H/D bonds. Finally, desorption of the alkane regenerates the
active catalyst material.
Scheme 4. Control experiments for the hydrogenation and deuteriation of 4-
allylanisole.
Table 3. Selective deuteration of alkenes to deuterium labeled alkanes
catalyzed by Ni@C-450 catalysta.
Scheme 5. Proposed possible mechanism for the deuteration of terminal
alkenes.
Reaction conditions: a0.5 mmol alkene, 20 mg catalyst, 1 bar D2. RT, 2 mL
methanol, 16 h. Conversion were determined by GC using hexadecane as
internal standard. Deuteration percentage of α or β positionweredetermined by
comparison of 1H NMR and 2H NMR.
Mechanistic studies
Catalyst stability and recycling
To rationalize the activity of our novel catalyst system
several controlexperiments were completed. First, we wanted to
exclude the possibility of additionaltransferhydrogenationsin the
presence of methanol, which was used in most experiments as
the solvent. As shown by reactions 1 and 2 in Scheme 4, the
reduced product 4-n-propylanisole was only formed in the
To prove the stability of this novel catalyst, several recycling
experiments were performed for the benchmark reaction using
different conditions. Indeed, Ni@C-450 can be reused
conveniently and after six times no significant loss of catalytic
activity isobserved at complete and lower conversion (Figure 3).
5
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10.1002/anie.202105492
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RESEARCH ARTICLE
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Here, we describe a novel nano-structured Ni-catalyst for
practical and convenient hydrogenation of various alkenes.
Calcination of simple Ni-saltson carbon support creates a highly
stable and reusable core-shellmaterial, which activateshydrogen
and deuterium alreadyat ambient conditions (room temperature,
1 bar). The optimal catalyst (Ni@C-450), showed excellent
activity and selectivity for the hydrogenation of terminal and
internal aliphatic and aromatic alkenes including functionalized
ones. Noteworthy, different deuterium-labeled alkanes can be
prepared using Ni@C-450 at room temperature in presence of 1
bar D2.
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Acknowledgements
We gratefully acknowledge the European Research Council(EU
project 670986-NoNaCat) and the State of Mecklenburg-
Vorpommern forfinancialand generalsupport. Jie Gao thanks the
China Scholarship Council(CSC) for financialsupport. We thank
the analytical staff of Leibniz-Institut für Katalyse e.V., Germany
and Dalian Instituteof ChemicalPhysics, China for theirexcellent
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Keywords: catalysis• nanoparticles• alkenes• hydrogenation •
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Entry for the Table of Contents
Hydronations and deuteration of olefins made easy: Core-shell structured Ni-nanocatalyst (Ni NPs@C) allows for the selective
hydrogenation and deuteration of alkenes under ambient conditions(1 bar H2 / D2, RT)
8
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