Study of CoCu Alloy Nanoparticles Supported on MOF-Derived Carbon for Hydrosilylation of Ketones

Article abstract of DOI:10.1007/s10562-019-03065-2

Abstract: Carbonized zeolitic imidazolate frameworks (ZIFs) show potential as mesoporous heterogeneous catalysts with high metal loadings. ZIF-67 and ZIF-8 were used to create mono- and bimetallic CoCu particles supported on nitrogen-doped carbon via self

Full text of DOI:10.1007/s10562-019-03065-2

Catalysis Letters
https://doi.org/10.1007/s10562-019-03065-2
Study of CoCu Alloy Nanoparticles Supported on MOF‑Derived Carbon
for Hydrosilylation of Ketones
David B. Christensen1 · Rasmus L. Mortensen1 · Søren Kramer1 · Søren Kegnæs1
Received: 4 October 2019 / Accepted: 2 December 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
Carbonized zeolitic imidazolate frameworks (ZIFs) show potential as mesoporous heterogeneous catalysts with high metal
loadings. ZIF-67 and ZIF-8 were used to create mono- and bimetallic CoCu particles supported on nitrogen-doped carbon
via self-assembly in methanol at room temperature, followed by carbonization at 675 °C. A Cu precursor, Cu(NO3)2·2H2O,
was impregnated into the ZIF-67 before carbonization to obtain bimetallic catalysts. Nanoalloy particles with diferent CoCu
ratio were synthesized and characterized using XRD. The materials were further characterized using TEM, SEM, XRF and
nitrogen physisorption. The diferent alloys were tested in conversion of cyclohexanone to the corresponding silyl ether.
Complete conversion of cyclohexanone at 90 °C for 24 h were obtained. The catalyst Co99Cu1@NC gave a 60% increase in
yield over a pure Co analogue.
Graphic Abstract
Keywords Hydrosilylation · MOF · ZIF-67 · Carbonization · Bimetallic alloy
1 Introduction
The synthesis of new heterogeneous catalysts containing
earth-abundant metals ofers a way to create cheaper, more
sustainable alternatives to more traditional catalysts con-
Electronic supplementary material The online version of this
taining precious metals like Pd, Pt or Ru [1–5]. One of the
article (https://doi.org/10.1007/s10562-019-03065-2) contains
challenges of using earth-abundant metals is that they usu-
ally have much lower activities compared to their precious
metal counterparts. This can often be circumvented by creat-
ing base metal nanoalloys [6–11]. According to Sabatier’s
Principle, there is an optimal adsorption energy between
the reactant and the active site. This is usually illustrated in
supplementary material, which is available to authorized users.
* Søren Kegnæs
skk@kemi.dtu.dk
1
Department of Chemistry, Technical University of Denmark,
Kemitorvet 207, 2800 Kgs. Lyngby, Denmark
Vol.:(0123456789)
1 3

D. B. Christensen et al.
the form of a volcano plot [12, 13]. An alloy will have an
adsorption energy somewhere in between its components.
Using this principle, alloys may achieve properties similar
or sometimes superior to those of pure precious metals [8,
14–16]. However, it can be challenging to synthesize the
desired alloyed nanoparticles in the right ratio and uniform
distributed in the catalyst.
a variety of loadings using ZIF-67 as a carbon-, cobalt-,
nitrogen-containing platform. Cobalt containing ZIF-67
was impregnated with a different Cu solution before car-
bonization. In total were seven different catalysts synthe-
sized with different amounts of cobalt and copper. The
synthesized materials were characterized using XRD,
TEM, SEM, XRF and nitrogen physisorption. The cata-
lytic activities of the produced materials were compared
using a model reaction, conversion of cyclohexanone to
the corresponding silyl ether. The reaction is typically
run using a homogenous precious metal catalyst [38–40].
The synthesis method benefts from the presence of nitro-
gen in the 2-methylimidazole in the ZIF, creating a natural
nitrogen-doping of the resulting carbon. Nitrogen-doping of
carbon is a common way of tuning the electronic properties
of carbon materials, often utilized in the development of
electro-catalysts for fuel cells and other electronic devices
[41]. However, the positive efect of nitrogen-doping is not
limited to electrochemical reactions as number of other
reactions have seen increased yield due to the presence of
nitrogen [42–46].
Metal–organic frameworks (MOFs) have attracted
a lot of attention recently, due to the ease of synthesis,
high porosity and surface area [17, 18]. MOFs are easily
made by mixing a metal salt with an organic linker in an
appropriate solvent. Recently, there has been interest in
the use of MOF derivatives as the structural template for
making a new class of heterogeneous catalysts [19–21].
MOF derived carbon materials have been known at least
since 2007, where MOF-5 was pyrolysed with polymer-
ized furfuryl alcohol to make a nanoporous carbon with
good hydrogen uptake and electrochemical properties
[22]. Since then, diferent types of MOF-derived nano-
materials have been tested for use in sensing, gas-/energy-
storage and catalysis with good performance [23, 24]. One
method is to carbonize the MOF, creating a carbonaceous
support material. Due to the high structural stability of the
original MOF, much of the structure, pore volume and spe-
cifc surface area is preserved after carbonization [25–27].
The material gains increased thermal and chemical stabil-
ity, but loses the functionalities of the ligands [28–30].
The carbonization process also help with the reduction of
the metal ions present in the ZIF structure to form metal
nanoparticles. MOF-derived carbons have been tested for
several purposes such as oxygen reduction reaction, Li-ion
batteries, gas storage and as a support material for hetero-
geneous catalysts [31–33].
2 Experimental Section
A total of seven types of catalysts were synthesized with
expected Co/Cu ratios of 99:1, 19:1, 9:1, 3:1, 1:1 as well as
a pure Co and pure Cu variant. The samples are labelled as
CoxCuy@NC, were x and y indicate the expected amount
of Co compared to Cu and NC = nitrogen-doped carbon.
According to the empirical formula, C8H10N4Co, the ZIF-
67 is expected to contain 26.7 wt% Co before carbonization,
which serves as the basis for the calculating the amount of
Cu needed. The basic procedure for ZIF-67 has been used
in previous work [37].
Zeolitic imidazolate framework (ZIF) materials are
a group of MOFs with attractive properties, due to their
structural similarities to zeolites [34, 35]. A great number
of ZIF structures have been reported over the last decade,
mimicking both known zeolite structures and added new
topologies [21, 35, 36]. Synthesis of ZIF with more than
one metal and with diferent metal ratios can be difcult and
time-consuming. By using incipient-wetness impregnating
on the porous ZIF with a secondary metal precursor before
carbonization, bimetallic alloy nanoparticles are expected to
be formed inside the new carbon support. Previously a 50/50
CoNi alloy has been synthesized using a similar procedure
[37]. Data from XRD indicated the formation of uniform
alloy nanoparticles between Co and Ni in the carbonized
ZIF-67.
2.1 Materials
All chemicals were obtained from Sigma-Aldrich with no
further purifcation. 2-methylimidazole, cobalt nitrate hexa-
hydrate (Co(NO3)2·6H2O>98%), methanol (MeOH≥99%),
zinc nitrate hexahydrate (Zn(NO3)2·6H2O≥99%), copper(II)
nitrate hemi(pentahydrate) (Cu(NO3)2·2.5H2O), cyclohex-
anone, dimethylphenylsilane (HSiMe2Ph ≥ 98%), toluene,
dibenzylether, ethylacetate, d-chloroform (CDCl3 99.8 atom
% D), triethylsilane (HSi(C2H5)3 99%).
Herein we present a simple way to synthesize
cobalt–copper nanoalloys on nitrogen-doped carbon in
1 3

Study of CoCu Alloy Nanoparticles Supported on MOF-Derived Carbon for Hydrosilylation of…
increased temperature is required in order to remove the
2.2 Synthesis of ZIF‑67 and ZIF‑8
Zn in the ZIF-8 and incorporate Cu in the structure.
ZIF-67 was synthesized according to previous work by Lou
et al. [47]. In a 1L Erlenmeyer fask a solution of 2-meth-
ylimidazole in MeOH (3.2840 g in 250 mL) and a solu-
tion of Co(NO3)2·6 H2O in MeOH (2.9104 g in 250 mL)
were mixed at room temperature. The mixture was stirred
for 5 min, aged for 24 h. The cobalt containing ZIF-67 was
collected by centrifugation and dried in an oven at 80 °C.
The typical yield was 0.5 g.
2.5 Material Characterization
XRF data was acquired using a PanAnalytical epsilon 3-XL
directly on the powdered catalyts without any prior treat-
ment. TEM images was acquired on a FEI Tecnai T20 G2
instrument from Thermo Fisher Scientifc. Powdered sam-
ples were placed on holey carbon grids with no prior treat-
ment. SEM was carried out on a FEI Quanta 200 ESEM
FEG on powdered samples placed on carbon grids. XRD
was acquired using Cu-Kα from a focusing quartz mono-
chromator and a Huber G670 Guinier camera. The samples
were loose powders and run for one hour.
ZIF-8 was synthesized using the same metal to ligand
ratio. A solution of 2-methylimidazole in MeOH (3.2840 g
in 250 mL) and a solution of Zn(NO3)2·6H2O in MeOH
(2.9748 g in 250 mL) were mixed at room temperature. The
mixture was stirred for 5 min, aged for 24 h. The zinc con-
taining ZIF-8 was collected by centrifugation and dried in
an oven at 80 °C. The typical yield was 0.8 g.
2.6 Catalytic Measurements
The catalytic performances of the catalysts were compared
using the hydrosilylation reaction of cyclohexanone. The
experiments used solutions of 1 mmol cyclohexanone/mL
and 1.2 HSiMe2Ph/mL in toluene prepared in glovebox
together with 10 mg CoxCuy@NC catalyst. The vials were
sealed with tefon caps and allowed to react outside the
glovebox at 90 °C, stirred at a rate of 600 RPM. The prod-
ucts were quantifed by NMR. 1H-NMR data was acquired
on a Bruker Ascend 400 (400 Hz).
2.3 Synthesis of CoxCuY@NC
Diferent amounts of Cu(NO3)2·2.5H2O were dissolved in
85 μL MeOH. Dried ZIF-67 was impregnated to incipient-
wetness to make each of the desired Co/Cu ratios. The
resulting powders were fushed at room temperature using
Ar for 30 min. followed by carbonization at 675 °C heated
at a rate of 5 °C/min. in Ar for 3 h.
2.4 Synthesis of Cu@NC
3 Results and Discussion
As a reference material Cu@NC was synthesized. A solu-
tion of Cu(NO3)2·2.5H2O in MeOH (45.4 mg in 340 μL)
was prepared. 170 μL of the solution was used for incipi-
ent wetness impregnation of the dried ZIF-8. The result-
ing powder was followed by flushing in Ar for 30 min.
at room temperature. The impregnated powder was then
carbonized at 900 °C heated at rate 5 °C/min. for 3 h. The
Each of the seven CoxCuy@NC catalysts synthesized were
characterized using a number of diferent techniques along
with the original ZIF-67 material for comparison.
In order to form the cobalt–copper alloyed particles
on nitrogen-doped carbon, the ZIF-67 impregnated with
Cu precursor was carbonized in Ar at high temperature.
Fig. 1 Schematic representation of a typical synthesis of Cu-doped carbonized ZIF-67
1 3

D. B. Christensen et al.
Fig. 2 N2-physisorption isotherm of synthesized ZIF-67 (a) and Co9Cu1@NC-675 (b)
The decomposition during carbonization was investigated
using TGA (see Supporting Information, S1). ZIF-67
starts to decompose at around 480 °C and has lost about
40% of its total mass at 600 °C. Based on ICP-OES the
content of pure ZIF-67 is about 26 wt% as is expected
from it empirical formular (C8H10N4Co). After carboniza-
tion at 600 °C, the Co content increases to about 30 wt%
(see Supporting Info, S2) (Fig. 1).
ZIF-67 shows a high surface area of 1364 m2/g (BET), and
a pore volume of 0.762 cm3/g (Single Point Adsorption)
similar to what has been reported in other work [19, 48].
After impregnation and carbonization, the surface area and
total pore volume drops signifcantly. Co9Cu1@NC-675 had
a BET surface area of 244 m2/g and a total pore volume of
0.079 cm3/g. BJH adsorption and comparison of isotherms at
diferent copper loadings can be found in Supporting Infor-
mation S3–S5.
Nitrogen physisorption of the synthesized ZIF-67 and the
derived carbon material is shown in Fig. 2. ZIF-67 originally
had a typical type I isotherm indicating a microporous mate-
rial. After impregnation with 10% copper and subsequent
carbonization, the isotherm becomes a type II with a clear
hysteresis loop indicative of mesopores in the structure.
The change in structure from ZIF-67 to porous carbon
support is apparent in SEM. In Fig. 3 it is clear that the
polyhedral shape of the original ZIF-67 is distorted after
Fig. 3 SEM images showing the polyhedral shape of the catalysts, which clearly seen for ZIF-67 (a), however it has been somewhat distorted
after carbonization at 675 °C as seen for Co9Cu1@NC (b)
1 3

Study of CoCu Alloy Nanoparticles Supported on MOF-Derived Carbon for Hydrosilylation of…
Co19Cu1@NC
Co99Cu1@NC
Co@NC
Co1Cu1@NC
Co3Cu1@NC
Co9Cu1@NC
Co19Cu1@NC
Co99Cu1@NC
Co@NC
Co1Cu1@NC
Co3Cu1@NC
Co9Cu1@NC
(b)
(a)
0
10
20
30
40
50
60
70
80
90
100
42.8 43.0 43.2 43.4 43.6 43.8 44.0 44.2 44.4 44.6 44.8 45.0
2θ (degree)
2θ (degree)
Fig. 4 XRD pattern of synthesized nitrogen-doped carbon catalyst. a
Shows the full range of angles measured, showing none of the many
characteristic peaks of ZIF-67 between 5 and 40°. b Features a zoom-
in on the Co(111) and Cu(111) peaks. The Co(111) is clearly seen
shifting downward at higher Cu loadings
Table 1 CoCu ratios determined using XRF
(111) peak, the particles were estimated to contain roughly
10% Cu. The Cu (111) peak is not notably shifted from the
location of pure copper, indicating the presence of pure
copper particles. Even with an equal amount of Co and
Cu, the nanoparticles seemingly consist of CoCu particles
containing 10% Cu and a larger amount of separate almost
pure Cu nanoparticles.
Entry
Catalyst
Cu(NO3)2·2.5H2O
Cu/Co ratio
added/100 mg ZIF-67
1
2
3
4
5
6
7
Co@NC
–
–
1/65.67
1/15.67
1/7.93
1/2.62
1/0.90
–
Co99Cu1@NC
Co19Cu1@NC
Co9Cu1@NC
Co3Cu1@NC
Co1Cu1@NC
Cu@NC
1.05 mg
5.55 mg
11.7 mg
35.1 mg
105.2 mg
–
Characterization using XRF was used to confrm the
CoCu ratio of the synthesized catalyst (see Table 1). The
results show good control over CoCu ratio using simple
incipient wetness impregnation. In general the amount of Co
is lower than expected. This may be due to a slightly lower
content of Co in the parent ZIF-67 material. The nitrogen
species present in the structure were examined using XPS
(see Supporting Info, S4 and S5). The nitrogen content in
the surface was found to be about 4% for the carbonized
ZIF (Entry 1), while the materials containing added copper
(Entry 2–6) had an increased content ranging from 7.8 to
11%. The nitrogen peaks indicated equal amounts of gra-
phitic and pyradinic nitrogen with the exception of Entry
1, which also showed a fair amount of pyrrolic nitrogen
(31.9%) and less graphitic nitrogen (12.5%).
impregnation with Cu and subsequent carbonization. The
overall particle size seems reduced from the original 1 μm
to about 700 nm.
XRD was performed to confrm the formation of CoCu
alloyed particles. Each of the catalysts (Fig. 4) show char-
acteristic peaks of Co at 44.32, 51.70, 75.8 and 92.1°. At
higher loadings of Cu, its (111) peak becomes visible at
43.31°, along with additional peaks at 50.4, 74.1, 89.9
and 95.2°. The Co (111) peak at 44.32° shifts towards a
lower difraction angle of 44.20°, when the metal con-
tent is above 25% Cu. None of the typical peaks associ-
ated with ZIF-67 between 5 and 40° can be seen here [42,
49]. The peaks were identifed using data from the ICDD.
According to Vegard’s Law, the location of the alloy peak
can be linearly related to its composition. Based on the Co
TEM images of the carbonized ZIFs show that the dodec-
ahedral shape of ZIF-67 is retained after carbonization
(Fig. 5). This matches what has previously been reported by
Zou et al. [50] The size of the dodecahedra’s range from 0.6
to 1.4 μm, seemingly increasing in size with higher loadings
of Cu. The metal nanoparticles are clearly seen distributed
1 3

D. B. Christensen et al.
across the carbon support. The size of the metal nanoparti-
cles mainly range from 8 to 20 nm.
TEM also shows the infuence of the higher Cu loading
on the overall structure of the carbon matrix. The dodecahe-
dral structure seemingly increases in size with higher load-
ings of Cu. As the amount of added Cu increases, the carbon
structure loses much of its dodecahedral structure as can
be seen from Co3Cu1@NC and Co1Cu1@NC. STEM–EDS
shows how the large particles generated when doping with
more Cu are mostly pure Cu particles, while at lower load-
ings a good dispersion of both Cu and Co is seen (see Sup-
porting Info, S13-14).
3.1 Hydrosilylation of Cyclohexanone
In order to compare the activities of the synthesized
CoxCuy@NC catalysts, the hydrosilylation of Cyclohex-
anone (1a) was chosen as a model reaction. The same
amount of catalyst was used for each of the reactions.
The results from the hydrosilylation of cyclohexanone
(1a) can be seen in Table 2. Using the carbon catalyst
derived directly from ZIF-67 (Entry 1) yields 21% of
the silyl ether product under the given conditions. The
purely copper containing Cu@NC derived from ZIF-8
(Entry 7) affords a much lower yield of only 9%. Similar,
low yields where observed for commercial Cu and Pt on
carbon (Supporting Info S17). A clear improvement in
reactivity is seen when the two are combined to form
CoCu alloy nanoparticles. Even Co99Cu1@NC shows an
increase in yield from 21 to 35% compared to Co@NC.
When using much higher Cu loadings like those found
Fig. 5 TEM images of all ZIF-67 derived catalysts. As more Cu
is added, the polyhedral structure starts to break down. a Co@NC,
b Co99Cu1@NC c Co19Cu1@NC d Co9Cu1@NC e Co3Cu1@NC f
Co1Cu1@NC. (Cu@NC can be found in Supporting Info S10–S12
along with histograms and additional images of all catalysts)
Table 2 Experimental results from hydrosilylation of cyclohexanone
OSiMe2Ph
O
8 mol% Catalyst
PhMe (1.0 M), 90 °C, 24 h
Me2PhSiH
1a
1 mmol
2a
1.2 eq.
Entry
Catalyst
Co@NC
Co99Cu1@NC
Co19Cu1@NC
Co9Cu1@NC
Co3Cu1@NC
Co1Cu1@NC
Cu@NC
Yield (%)
Conversion (%)
1
2
3
4
5
6
7
21
35
38
72
100
100
9
38
41
45
72
100
100
29
Yield based on NMR
1 3

Study of CoCu Alloy Nanoparticles Supported on MOF-Derived Carbon for Hydrosilylation of…
brought the yield down to a few percent (1b). Acetophe-
80
60
40
20
0
none readily reactants to form the silyl ether. Induction
effects affects the yield as demonstrated by the addition
of different groups in the para position. A methyl group
brings the silyl ether yield down to 75% (1d). The combi-
nation of a longer alkyl chain on the ketone and an ether
group in the para position lowers the yield down to 57%
(1e). The introduction of electron withdrawing group,
fluorine, brings the yield down to 46% (1f). Addition-
ally, when a large bulky group was added at the end of the
alkyl, the yield was lower than for any of the other ace-
tophenones (1g). TEM of the Co9Cu1@NC after reaction
show no notable differences to the fresh catalyst (Sup-
porting Info, S15-16). The catalyst show partly deactiva-
tion when reused first time. However, the deactivation
seemed to stabilise when reused further times (Supporting
S18).
0
5
10
15
20
25
Time (hours)
Fig. 6 Time study of Co9Cu1@NC for the hydrosilylation of
cyclohexanone
4 Conclusion
in Co3Cu1@NC and Co1Cu1@NC complete conversion
is achieved.
MOF derived carbon materials combine the advantages of
a stable porous materials with a high metal loading. The
present work shows that using simple preparation meth-
ods, bimetallic CoCu alloy nanoparticles incorporated in
mesoporous carbon can be synthesized with good control
of the metallic ratio. The nanoparticles are well-distributed
with an average size of about 10 nm. The CoxCuy@NC675
catalysts show high yield for a simple hydrosilylation reac-
tion compared to catalysts containing only Co or Cu. Under
relatively mild conditions, complete conversion of cyclohex-
anone to the silane when the CuCo ratio is 1/2.62 or above.
Co9Cu1@NC was selected for a time study (Fig. 6) and
scope for a range of hydrosilylation reactions (Table 3).
The time study shows the reaction occurs with no induc-
tion period and fits with an overall 1st order reaction
(Fig. 7). Cyclohexanone (1a) gave good yields under
these conditions. However, the addition of a t-butyl group
Table 3 Experimental results
from substrate scope of
OSiMe2Ph
O
8 mol% Co9Cu1@NC
hydrosilylation using Co9Cu1@
Me2PhSiH
1.2 eq.
NC
R
R
R
R
PhMe (1.0 M), 90 °C, 24 h
2a-g
1a-g
O
O
O
O
Yield
72%
Yield
1%
Yield
Yield
91%
32%
Yield
75%
1a
1b
1c
1d
O
O
O
O
Yield
F
Yield
57%
46%
1e
1f
1g
Yield based on NMR
1 3

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Acknowledgements The authors are grateful for funding from the
Independent Research Fund Denmark (Grant No. 6111-00237), from
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Compliance with Ethical Standards
Conflict of interest The authors declare that they have no confict of
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