Supported Cobalt Nanoparticles for Hydroformylation Reactions

Article abstract of DOI:10.1002/chem.201806282

Hydroformylation of olefins has been studied in the presence of specific heterogeneous cobalt nanoparticles. The catalytic materials were prepared by pyrolysis of preformed cobalt complexes deposited onto different inorganic supports. Atomic absorption spectroscopy (AAS) measurements indicated a correlation of catalyst activity and cobalt leaching as well as a strong influence of the heterogeneous support on the productivity. These new, low-cost, easy-to-handle catalysts can substitute more toxic, unstable and volatile cobalt carbonyl complexes for hydroformylations on a laboratory scale.

Full text of DOI:10.1002/chem.201806282

A Journal of
Accepted Article
Title: Supported Cobalt Nanoparticles for Hydroformylation Reactions
Authors: Maximilian Franz Hertrich, Florian Korbinian Scharnagl,
Anahit Pews-Davtyan, Carsten Kreyenschulte, Henrik Lund,
Stephan Bartling, Ralf Jackstell, and Matthias Beller
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To be cited as: Chem. Eur. J. 10.1002/chem.201806282
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Supported by

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10.1002/chem.201806282
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Supported Cobalt Nanoparticles for Hydroformylation Reactions
[
a]+
[a]+
[a]
Maximilian Franz Hertrich, Florian Korbinian Scharnagl, Anahit Pews-Davtyan, Carsten
[
a]
[a]
[a]
[a]
[a]
Kreyenschulte, Henrik Lund, Stephan Bartling, Ralf Jackstell and Matthias Beller*
Abstract: Hydroformylation of olefins has been studied in the
presence of specific heterogeneous cobalt nanoparticles. The
catalytic materials were prepared by pyrolysis of preformed cobalt
complexes deposited onto different inorganic supports. AAS-
measurements indicate a correlation of catalyst activity and cobalt
leaching as well as a strong influence of the heterogeneous support
on the productivity. These novel, low-cost, easy to handle catalysts
can substitute more toxic, unstable and volatile cobalt carbonyl
complexes for hydroformylations on lab-scale.
To overcome these limitations, immobilisation of metal
complexes, for instance, was introduced with supported
[
24-28]
ionic liquid-phase (SILPs) systems.
Other methods
attempted to build a bridge between homogeneous and
heterogeneous catalysis by the formation of dispersed
[29-31]
single metal atom catalysts (SACs)
or small
[32-33]
nanoparticles (NPs).
In past years, our group developed several nanoscale
catalysts, especially based on N-doped carbon supported
cobalt- and iron-species. Those catalysts are easily
®
prepared by pyrolysis of a carbon source such as Vulcan
Introduction
[
34-35]
[36-
XC 72R, impregnated with in situ ligated Co
and Fe,
3
7]
respectively. Similar materials containing nanoparticles
Regarding scale, hydroformylation of olefins constitutes
[
38]
supported on inorganic carriers
and biomass-derived
Based on these works,
the
most
important
homogeneously
catalysed
[
39-41]
[
1-2]
catalysts were studied, too.
methodology.
The resulting aldehydes are easily
herein we describe the synthesis for cobalt-containing
materials and studied their catalytic performance in
hydroformylation reactions.
transformed into esters, alcohols, carboxylic acids, and
aliphatic amines, which are widely used as intermediates
for plasticizers, solvents, detergents and fine chemicals. In
industry, until to date only cobalt- and rhodium-based
homogeneous catalysts are applied, even though
[
3]
Results and Discussion
alternative metals continue to attract significant attention.
Since the 1970´s, for lower olefins (<C ) cobalt carbonyl
5
Preparation of and Structural Trends for the Materials
complexes have been replaced by phosphine- or phosphite-
modified rhodium systems, which possess superior activity
Initially, we prepared around 50 materials based on a
[
34]
[
4-5]
general procedure developed by our group.
For this
and selectivity.
On the other hand, cobalt catalysts are
purpose, different commercially available supports (e.g.
carbon, titania, silica, ceria, alumina) were impregnated with
cobalt(II) acetate in the presence of different N-containing
organic ligands (2 eq.). Subsequent pyrolysis, in general at
mainly applied for the conversion of mid- and long-chained
olefins to alcohols due to their inherent high hydrogenation
activity.
Notably, for both cases costs for metal/ligands or
recycling are decisive. Hence, there is a growing interest to
develop more economic technologies, which allow
800 °C, led to
a
library of catalysts named
Co/Ligand@Support.
Detailed descriptions of the
[
6]
preparation method, thermo-gravimetric analyses for the
two mainly used ligands as well as for the preparation of
Co/phen@C, the analytical methodologies, and the
characterisation of selected materials are given in the
supporting information.
quantitative catalyst recycling.
In this respect, many
research groups investigated both heterogeneous and
immobilised homogeneous catalysts for the title reaction,
[
7-14]
[15-17]
mainly using rhodium,
but also cobalt systems
as
[
18-23]
well as other metals.
The main problem of all these
The general compositions of selected catalysts were
studied by powder X-ray diffraction (XRD) experiments and
elementary analysis (EA) while the surface structures for
some supported nanoparticles were characterised in more
detail by X-ray photoelectron spectroscopy (XPS) or
transmission electron microscopy (TEM). All supported
cobalt nanoparticles are either core shell structured with a
cobalt core and a closed cobalt oxide shell or a pure cobalt
oxide or metallic cobalt phase, respectively. In some cases
graphene layers covering big particles were observed.
Remarkably, no clear correlation between cobalt content or
oxidation state of the cobalt species at the surface and
catalytic activity of the materials could be ascertained.
catalysts is the leaching of active metal-species from the
support in the presence of CO. Furthermore, both activity
and selectivity of heterogenized catalysts are in general
lower compared to their homogeneous counterparts.
[
a]
Maximilian Franz Hertrich, Florian Korbinian Scharnagl, Anahit
Pews-Davtyan, Carsten Kreyenschulte, Henrik Lund, Stephan
Bartling, Ralf Jackstell and Matthias Beller
Leibniz-Institut für Katalyse e.V. an der Universität Rostock
Albert-Einstein-Straße 29a, D-18059 Rostock, Germany.
These authors contributed equally to this work.
+
*
Corresponding E-Mail-adress: matthias.beller@catalysis.de
Supporting Information (SI): General experimental procedures,
characterisation data and NMR spectra are available. See DOI:
10.1039/x0xx00000x
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Chemistry - A European Journal
10.1002/chem.201806282
FULL PAPER
syngas (CO : H
2
= 1 : 1) at 100 °C for 18 hours. To compare the
As ligands, inexpensive compounds such as urea, typical
pyridine derivatives, but also biologically relevant
nucleobases, amino acids, and even biopolymers (chitosan
activity of our systems with the “corresponding” homogeneous
one, we carried out experiments with dicobalt octacarbonyl as
pre-catalyst, as well (Table 1, entry 1).
[
42]
and chitin) were used. Notably, chitosan is produced via
deacetylation of chitin, simply obtained from shrimp or crab
In general, the conversion of n-butyl acrylate in
hydroformylation should be faster than the conversion of
neohexene. Indeed, when dicobalt octacarbonyl was used as
pre-catalyst this prediction was confirmed (Table 1, entry 1). The
reason for that is the steric demand of the tert-butyl group in
neohexene on the one hand and the electronic activation of the
double bond by the ester group in n-butyl acrylate on the other
hand. Following this trend, all catalysts based on the
phenanthroline precursor were less active in neohexene
hydroformylation than for the reaction of n-butyl acrylate (Table
[
43-45]
shells.
It is known to form stable complexes with metal
and it was found to be an excellent precursor for
[
46-47]
ions
[
48-49]
N-doped graphene.
Previously, both chitosan- and
phenanthrolin-based materials exhibited good performance
[
39-41]
in catalytic hydrogenation reactions;
especially on these systems.
thus, we focused
Catalytic Activity
1
, entries 2, 4, 6, 8). Conversely, the catalysts prepared with the
We started to explore the activity of the cobalt catalysts in
two hydroformylation reactions (Table 1). Neohexene (tert-
butyl ethylene) and n-butyl acrylate were chosen as model
substrates. In the first case, the hydroformylation was
chitosan precursor showed the opposite behaviour (Table 1,
entries 3, 5, 7). This finding is remarkable and contrary to
general expectations. Obviously, the support of the catalyst as
well as the ligand has an important influence on the activity.
As a general trend for the hydroformylation of neohexene we
expected to yield regioselectively the linear aldehyde
2 as
product due to the steric demand of the tert-butyl group.
found that the ceria supported catalysts Co/phen@CeO
2
and
Co/Chitosan@CeO (Table 1, entries 2 and 3) showed the
lowest activity compared to the other materials based on the
respective precursor. The phenanthroline derived catalyst
2
Table 1. Hydroformylation of neohexene and n-butyl acrylate catalyzed by
cobalt nanoparticles on different supports.
2
supported on silicon dioxide Co/phen@SiO was slightly more
productive in neohexene hydroformylation (Table 1, entry 4).
Best activity for the phenanthroline based materials was reached
2
with Co/phen@C, followed by Co/phen@TiO (Table 1, entries 6
and 8). However, the conversion rates for that type of catalysts
were not higher than 55% (Table 1, entry 6) and product yields
did not exceed 45% (Table 1, entry 8). Comparing materials
resulting from the pyrolysis of chitosan, we found that the silicon
dioxide support led to the best performance (52% conversion
and 46% yield; Table 1, entry 5), comparable to that of
Co/phen@C. The corresponding material based on titania
a
a
b
conv.
1
yield
2
conv.
3
yield
linearity
Entry
catalyst
4a + 4b 4a, 4b
2
Co/Chitosan@TiO was less active (Table 1, entry 7).
1
2
Co (CO)
58%
4%
51%
1%
>99%
8%
92%
2%
95%
>99%
>99%
2
8
While the phenanthroline based catalysts are more active in
the hydroformylation of n-butyl acrylate compared to the
corresponding chitosan derived materials, there is no clear trend
observed for neohexene hydroformylation. Among the different
supports, cobalt on ceria gave the lowest conversions and yields
Co/phen@CeO2
Co/Chitosan@CeO2
22%
22%
52%
55%
46%
53%
17%
18%
46%
38%
36%
45%
2%
2%
3
4
Co/phen@SiO2
81%
47%
60%
33%
82%
31%
83%
95%
95%
95%
98%
96%
Co/Chitosan@SiO2
5
6
(
Table 1, entries 2 and 3). In fact, the two ceria supported
catalysts are almost inactive. Most suitable for catalysing n-butyl
acrylate hydroformylation are Co/phen@TiO and Co/phen@C
Table 1, entries 6 and 8). Both showed full conversion of n-butyl
acrylate and over 80% yield. In the case of the chitosan
catalysts Co/Chitosan@SiO gave the highest conversion rate
47%) and a yield of 33% (Table 1, entry 5), followed by the
titania supported Co/Chitosan@TiO (Table 1, entry 7).
Co/phen@TiO2
>99%
40%
Co/Chitosan@TiO2
2
7
8
(
Co/phen@C
>99%
2
Standard reaction conditions: neohexene (1) (193 µL, 1.5 mmol) or n-
butyl acrylate (3) (214 µl, 1.5 mmol), catalyst (29.5 mg), toluene (1.5 mL),
(
a
4
0 bar CO/H
2
(1:1), 100 °C, 18 h. Conversions and yields represent the
2
mean value of three experiments and were calculated by GC using
hexadecane as internal standard. Linearity represents the amount of 4a
with respect to the total amount of linear and branched aldehyde (4a +
As by-products, we observed in all reactions the
corresponding alkanes. In the case of n-butyl acrylate we could
also detect some dimerisation by-product.
In addition, we tested all catalysts of our library. In general, the
catalysts based on other ligands than chitosan or phenanthroline
did not show an improved activity. Furthermore, the reaction
conditions were varied to study the influence of temperature,
pressure, and solvent amount in the presence of the most active
catalysts. An overview of these experiments is given in the
b
4b).
As an example of an electronically activated olefin, n-butyl
acrylate was selected to study the n/iso selectivity. In both
cases unwanted isomerization reactions cannot take place.
We decided to perform the reaction under a pressure of 40 bar
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Chemistry - A European Journal
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supporting information (Table S 3). At 85 °C the rate of
hydroformylation of both olefins was significantly declined. The
performance for hydroformylation of neohexene could be
improved by increasing the reaction temperature to 120 °C or
Actually, after 18 hours the substrate is completely converted
and the yield of aldehydes remained stable at a level of about
85%. In contrast, for the two least productive catalysts
2 2
Co/phen@CeO and Co/chitosan@TiO we found out that there
1
40 °C, respectively. Solvent concentration had only minor
is an induction period of at least six hours where the systems
are not active. Even after twelve hours the conversion rates and
yields are not higher than 10% for both materials.
influence on the catalysis, however, under neat conditions the
selectivity was rather low. Using butyl acrylate the reaction was
also scaled up by a factor of 10 leading to similar results (see
supporting information experimental methods).
To proof the general suitability of Co/phen@C for other
hydroformylations, we investigated reactions of 1-octene (5) and
cyclohexene (10) as linear and cyclic aliphatic compounds,
styrene (8) as an aromatic compound, N-vinyl phthalimid (9) and
diisobutene (7) as industrial relevant substrates, and 1,1-
diphenyl ethylene (6) as a sterically hindered one. The results of
this substrate scope are summarised in Scheme 1.
Figure 1. Conversion rates (dark colours) and yields (bright colours) for
hydroformylation of n-butyl acrylate after a certain reaction time with
three different catalysts. Standard reaction conditions: n-butyl acrylate
(
1
1.5 mmol), catalyst (29.5 mg), toluene (1.5 mL), 40 bar CO/H
00 °C. Conversions and yields were calculated by GC using
hexadecane as internal standard. Key: dark red/red graphs represent
conversion/yield with catalyst Co/phen@TiO , dark green/green graphs
represent conversion/yield with catalyst Co/chitosan@TiO
blue/blue graphs represent conversion/yield with
Co/phen@CeO
2
(1:1),
2
2
and dark
catalyst
2
.
Scheme 1. Standard reaction conditions: substrate (1.5 mmol), catalyst
(
29.5 mg), toluene (1.5 mL), 40 bar CO/H
2
(1:1), 100 °C, 18 h.
2
Although the activity of Co/chitosan@TiO and the yield and
Conversion of 5-10, the yielded products and the linearity represent the
conversions were rising after this induction period, the
productivity of the catalysts decreased again after 18 hours and
no higher yields than 32% were detected after 24 hours reaction
mean value of two experiments and were calculated by GC using
1
hexadecane as internal standard *or calculated by
H
NMR
measurements using 1,4-dimethoxybenzene as internal standard.
2
time. Co/phen@CeO showed a slightly different behaviour: For
the whole investigated period there seemed to be the same
activity after the induction period. However, the overall
Except for the sterically hindered 6, we observed mediocre to
good yields for the generated aldehydes. The hydrogenation of
the olefins to the corresponding alkanes is a competitive
pathway in some cases. In fact, for 6 and 8 1,1-diphenyl ethane
and ethyl benzene were detected as major products.
productivity of Co/phen@CeO
4 h).
It is well known in literature that heterogeneous metal catalysts
2
was very low (5% yield after
2
are leaching under typical condition of hydroformylation. In those
cases the active species – usually a metal carbonyl – is formed
Kinetic Behaviour and Leaching
[
50-53]
in situ.
Since the reaction solutions were normally coloured
For a better understanding for the activity of the catalytic
materials, we investigated the kinetic behaviour of our systems
as well as the metal leaching of the catalysts for
hydroformylation of n-butyl acrylate under the standard
conditions. Therefore, we determined the conversion rates and
yields after different reaction times from six hours up to 24
hours. The results of these experiments are summarised in
after stopping the reaction, we presumed that this colour
originated from leached cobalt carbonyl species. Indeed,
recycling of the catalyst Co/phen@C via filtration and washing
resulted in a significant drop of the productivity. For example,
only 8% product yield was detected after the third run compared
to 58% after the first cycle (see supporting information Table
S 4).
Consequently, we decided to study the amount of cobalt in the
reaction solutions after stopping the hydroformylation at certain
times (6, 12, 18, and 24 hours). For this purpose, the reaction
mixtures were filtered immediately after opening the reactor. All
volatile components were removed and the residues were
dissolved in aqua regia. Afterwards, the cobalt content of these
Figure 1. We chose three catalysts
–
one with low
with moderate
green graphs) and one with high
, red graphs). For Co/phen@TiO
2
(
(
Co/phen@CeO
Co/chitosan@TiO
2
,
blue
graphs),
one
2
,
productivity (Co/phen@TiO
2
we saw a growing activity until the twelfth hour of the reaction.
After that point the activity declined due to saturation effects.
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Chemistry - A European Journal
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aqueous solutions was determined via AAS. The results of this Conclusions
2
analysis for Co/phen@TiO (red graph), Co/phen@C (orange
graph), Co/chitosan@TiO
2
, (green graph) and Co/phen@CeO
2
In summary, we prepared several Co-containing materials by
pyrolysis and demonstrated their performance in several
hydroformylation reactions. The kinetic behaviour and the rate of
leaching of the catalysts depend strongly on the support and in
(
blue graph) are shown in Figure 2.
situ generated cobalt complex. As
a
result of these
investigations, we assume that the presented hydroformylation
reactions take place mainly in solution. Nevertheless, active
centres on the surface are productive to a limited extent, too. In
2
general, both Co/phen@TiO and Co/phen@C represent stable,
non-volatile and easy to handle reservoirs for active
homogeneous cobalt species, and thus can conveniently
substitute the common but toxic dicobalt octacarbonyl complex
in hydroformylations on small scale. Further investigations to
find more stable heterogeneous catalysts for hydroformylation
are ongoing in our group.
Experimental Section
Figure 2. Amount of leached cobalt after a certain time with four different
catalysts. Standard reaction conditions: n-butyl acrylate (1.5 mmol),
catalyst (29.5 mg), toluene (1.5 mL), 40 bar CO/H
2
(1:1), 100 °C. Cobalt
Catalytic Experiments
mass was calculated based on AAS-analysis of the fused reaction
solutions. Key: red graph represents cobalt in solution with catalyst
Typically, the catalytic experiments were carried out in 4 mL
glass vials. The vials were filled with 1.5 mL toluene, 193 µL
neohexene (1.5 mmol) or 214 µL n-butyl acrylate, 29.5 mg of the
catalyst (corresponding to 1 mol% of Co) and a glass-coated
stirring bar and closed with a septum cap. In order to allow gas
exchange, a needle was pierced through the septum. The vials
were placed on a steel plate in a 300 mL steel autoclave. The
closed reactor was washed three times with syngas and filled
Co/phen@TiO
Co/phen@C, green graph represents cobalt in solution with catalyst
Co/chitosan@TiO and blue graph represents cobalt in solution with
catalyst Co/phen@CeO
2
, orange graph represents cobalt in solution with catalyst
2
2
.
Obviously, the amount of cobalt in solution correlates to some
degree with the productivity of the catalysts. Independent of the
reaction time, the leaching of Co/phen@CeO
level as well as the activity of this catalyst. The amount of cobalt
deliberated from the other investigated catalysts Co/phen@TiO
Co/phen@C and Co/chitosan@TiO is increasing with the
reaction time and seemed to be saturated after 18 hours. For
these three materials no clear correlation between leaching and
productivity could be ascertained. On the one hand, Co/phen@C
2
remains on a low
with 40 bar syngas (H :CO = 1:1). The reaction was performed
2
for 18 hours at 100 °C while stirring (700 rpm to 800 rpm) the
reaction mixtures. After stopping the reaction via cooling of the
autoclave, the gas was released. The vials were moved out of
the autoclave and hexadecane as standard was added to the
reaction solution. After diluting with acetone, ethyl acetate or
toluene the grey to black suspension was filtered through a
syringe filter. Yields and conversion rates were calculated by GC
analysis with hexadecane as internal standard.
2
,
2
and Co/phen@TiO
and yield after 18 hours (see Table 1). In contrast to that, the
amount of leached cobalt is twofold higher for Co/phen@TiO as
2
showed almost same results for conversion
2
for Co/phen@C. On the other hand, the detected values for
cobalt in solution for the reaction with Co/phen@C and
Co/chitosan@TiO are at the same level, whereas the activity of
2
Proof of Leaching
For proof of leaching, the filtered reaction solution
(
hydroformylation of n-butyl acrylate) was transferred into a
both materials for hydroformylation differs not proportionally.
Interestingly, there is no correlation between cobalt content at
the surface and amount of leached cobalt, as well (see
supporting information).
These results demonstrate that both precursor and support of
the catalyst have an influence on metal leaching. Notably,
adding the commercial support material silica or titania to the
active homogeneous catalyst, resulted in a strong decline of the
catalyst activity, whereas addition of carbon or ceria did not
show any influence on the performance (see supporting
information Table S 4).
pressure tube. All volatile components of the solution were
removed under reduced pressure and 6 mL of aqua regia
(
3
HNO :HCl = 1:3) were added to the residue. The pale yellow
mixture was heated up to 140 °C for 4 hours in the closed
pressure tube. The resulting red-brownish solution was cooled
down to room temperature and then diluted with 6 mL of water.
After that, air was funnelled through the solution to remove all
nitrogen oxides, the solution was filled with water up to 25 mL
and was analysed by AAS.
Kinetic Experiments
For the kinetic experiments, the reaction protocol was the
same as for the catalytic experiments. The reaction time was
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Chemistry - A European Journal
10.1002/chem.201806282
FULL PAPER
decreased to 6 or 12 hours or increased to 24 h, respectively.
The work-up and the analytic procedure were the same as
described before.
[
[
13] C. Li, W. Wang, L. Yan, Y. Ding, Front. Chem. Sci. Eng. 2018,
12, 113-123.
14] D. Gorbunov, D. Safronova, Y. Kardasheva, A. Maximov, E.
Rosenberg, E. Karakhanov, ACS Appl. Mater. Interfaces 2018,
10, 26566-26575.
Acknowledgements
[
[
[
[
[
15] X. Song, Y. Ding, W. Chen, W. Dong, Y. Pei, J. Zang, L. Yan,
Y. Lu, Appl. Catal., A 2013, 452, 155-162.
This work was part of the KataPlasma project (MatRessources
program) funded by the German Federal Ministry of Education
and Research (BMBF). NoNaCat program and the federal state
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gratefully
1
04, 48-54.
18] G. Parrinello, J. K. Stille, J. Am. Chem. Soc. 1987, 109, 7122-
127.
acknowledged for financial funding. We thank Dr. Annette-Enrica
Surkus for fruitful discussions and her useful advice for the
preparation of heterogeneous catalysts. Dr. Giovanni Agostini is
acknowledged for his XPS measurements. We thank Alexander
Wotzka for conducting TGA measurements. The support of the
analytical department of the LIKAT and the University of Rostock
especially for the elementary analysis is recognised with thanks.
7
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Keywords: hydroformylation • cobalt • heterogeneous catalysis •
aldehydes • carbonylation • leaching
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Entry for the Table of Contents
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We report a new class of low-cost,
easy to handle materials for lab-
scale hydroformylation. The pyrolysis
of preformed Co complexes
deposited onto inorganic supports
resulted in immobilized cobalt
Maximilian Franz Hertrich, Florian
Korbinian Scharnagl, Anahit Pews-
Davtyan, Carsten Kreyenschulte,
Henrik Lund, Stephan Bartling, Ralf
Jackstell and Matthias Beller*
nanoparticles for oxo synthesis. The
Page No. – Page No.
most active materials Co/phen@TiO
and Co/phen@C represent
convenient reservoirs for active
homogeneous cobalt species, and
thus can substitute the common but
toxic dicobaltoctacarbonyl complex.
2
Supported Cobalt Nanoparticles for
Hydroformylation Reactions
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