Nickel Nanoparticles Supported on CMK-3 with Enhanced Catalytic Performance for Hydrogenation of Carbonyl Compounds

Article abstract of DOI:10.1002/ejic.201600318

Ordered mesoporous carbon materials are becoming increasingly important in catalysis applications due to their advantageous stability and surface properties. In this paper, we report a replication of the synthesis of mesoporous carbon CMK-3 using SBA-15 as a silica template. Ni/CMK-3 was prepared by incorporating Ni particles formed inside the pores of CMK-3 by impregnation of nickel nitrate and subsequent hydrogen reduction. The prepared Ni/CMK-3 has a large surface area and a very small nickel nanoparticle size (1 nm) with the aim of achieving high performance in catalytic hydrogenation reactions. Moreover, we demonstrate that CMK-3 has a higher stability than that of SBA-15 during the hydrogenation reactions of acetophenone derivatives.

Full text of DOI:10.1002/ejic.201600318

DOI: 10.1002/ejic.201600318
Full Paper
Nickel Nanoparticle Catalysts
Nickel Nanoparticles Supported on CMK-3 with Enhanced
Catalytic Performance for Hydrogenation of Carbonyl
Compounds
Daeho Kim,[a][‡] Hyuntae Kang,[a][‡] Hyesu Park,[a] Sungkyun Park,[b] Ji Chan Park,*[c] and
Kang Hyun Park*[a]
Abstract: Ordered mesoporous carbon materials are becoming hydrogen reduction. The prepared Ni/CMK-3 has a large surface
increasingly important in catalysis applications due to their ad-
vantageous stability and surface properties. In this paper, we
report a replication of the synthesis of mesoporous carbon
CMK-3 using SBA-15 as a silica template. Ni/CMK-3 was pre-
pared by incorporating Ni particles formed inside the pores of
CMK-3 by impregnation of nickel nitrate and subsequent
area and a very small nickel nanoparticle size (1 nm) with the
aim of achieving high performance in catalytic hydrogenation
reactions. Moreover, we demonstrate that CMK-3 has a higher
stability than that of SBA-15 during the hydrogenation reac-
tions of acetophenone derivatives.
Introduction
ports include ordered mesoporous carbons (OMCs),[6] carbon
nanotubes (CNTs),[7] and carbon nanofibers (CNFs).[8]
The discovery of nanoparticles (NPs) of various structures, sizes,
shapes, and compositions has opened up new possibilities.
These NPs have various advantages and could potentially influ-
ence the field of catalysis.[1,2] As the catalytic activity increases
with the reaction surface area of the catalyst, the diameter of
catalyst particles should be decreased to enhance the catalytic
activity. In other words, the enhancement of the specific activity
of metal NPs requires a reduction in particle size.
The stability of the catalyst support in the chemical environ-
ment is of great significance in the development of new sub-
strates. In addition to high surface area and porosity, uniform
pore size distribution, and high thermal stability, aggregation
resistance is also an important consideration in the appropriate
selection of a good catalyst support. Otherwise, the morphol-
ogy of the catalyst particles is changed, and the primary state
will result in a loss of catalytic activity. Carbon materials have
an excellent combination of stability and various surface prop-
erties.[3–5] Examples of carbon materials used to produce sup-
OMCs have recently received great attention since their dis-
covery in 1999.[9–13] They have high specific surface areas, con-
trollable pore sizes, and high electric conductivities.[14,15] OMC
materials are generally synthesized by a nanocasting route us-
ing various types of mesoporous silica as hard templates. These
OMCs have regular mesopores with sizes of 2–10 nm and ex-
hibit high surface areas of over 2000 m2 g–1.[16,17] Because of
these structural characteristics, OMCs have attracted much at-
tention as a new class of porous carbon material in the field of
catalysis, adsorption, and catalyst supports.[18–23] In particular,
OMC-supported metal NP catalysts show promising activities
in the Heck and Ullmann coupling reactions, as well as in the
hydrogenation reaction.[24–26]
The catalytic hydrogenation of carbonyl compounds to the
corresponding alcohols is undoubtedly one of the most impor-
tant organic reactions in the manufacture of chemicals, phar-
maceuticals, flavoring substances, and cosmetics.[27] These cata-
lytic hydrogenations provide considerable advantages including
easy-to-handle reagents, environmental friendliness, and mild
reaction conditions compared to those of other organic reac-
tions.[28,29]
[a] Department of Chemistry and Chemistry Institute for Functional Materials,
Pusan National University,
Busan 609-765, Korea
chemistry@pusan.ac.kr
http://www.chemistry.or.kr
In this work, we report the synthesis of a mesoporous silica
SBA-15 using the hydrothermal method and a mesoporous car-
bon CMK-3 replicated using SBA-15 as the silica template. These
mesoporous materials were tested in the hydrogenation of
carbonyl compounds after their stability had been investigated.
Liquid-phase hydrogenation of acetophenone in the presence
of CMK-3 on carbon-supported Ni (Ni/CMK-3) catalysts was car-
ried out under mild conditions. In addition, the stability of Ni/
[b] Department of Physics, Pusan National University,
Busan 609-735, Korea
[c] Clean Fuel Laboratory, Korea Institute of Energy Research,
Daejeon, 305-343, Korea
https://www.researchgate.net/profile/Ji_Chan_Park
[‡] These authors contributed equally to this work.
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejic.201600318.
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CMK-3 was compared to that of SBA-15 and to activate carbon initial CMK-3 support (1.46 cm3 g–1). Applying the Barrett–
support-catalysis.
Joyner–Halenda (BJH) method on the desorption branches, the
size of the small pores, which were obtained from the desorp-
tion branches in bare CMK-3 and in Ni/CMK, was found to be ca.
6 nm (Figure 2b). In addition, the small-angle X-ray diffraction
(SAXRD) pattern of CMK-3 shows (100), (110) and (200) reflec-
tions of a 2D hexagonal pore system.[30] However, (110) and
(200) reflections of Ni/CMK-3 were imperceptible, and the main
diffraction signal (100) was decreased, suggesting that during
the impregnation process, the pores of CMK-3 are partly
blocked or destroyed because of Ni nanoparticles (Figure S1 in
the Supporting Information). These results exactly match those
of other reported similar researches.[31,32]
Results and Discussion
Preparation of Ni/CMK-3 Catalyst
The OMC material CMK-3 was synthesized by a nanocasting
route using SBA-15 silica as reported in the literature. Ni/CMK-
3 was prepared by incorporating Ni particles formed inside the
pores of CMK-3 by impregnation of nickel nitrate and subse-
quent hydrogen reduction. For a uniform Ni particle dispersion
in the supported catalyst, Ni was loaded in approximately
10 wt.-%, on the basis of Ni converted from the nickel nitrate
salt after thermal treatment. The TEM image indicates that the
Ni nanoparticles were incorporated well into the mesopores of
CMK-3 (Figure 1, a). The high-angle annular dark-field scanning
transmission electron microscopy (HAADF-STEM) image also
shows regions of varying brightness. Relatively bright spots that
correspond to Ni particles can be observed (Figure 1, b). The
magnified HADDF-TEM image of the green square in Figure 1
(b) clearly shows a uniform dispersion of nickel particles (Fig-
ure 1, c). In the elemental mapping, carbon (blue) and nickel
(red) are confirmed (Figure 1, d–f). In the XRD pattern, Ni/CMK-
3 is well matched with that of metallic nickel in the cubic phase
(Figure 1, g; JCPDS no. 04-0850). The broad and intense peak
at 2θ = 44.5° corresponds to the (111) plane of Ni. The mean
particle size was estimated to be 1.6 nm using the Debye–
Scherrer equation from the full width at half maximum (fwhm)
of the (111) peak.
Figure 2. (a) N2 adsorption–desorption isotherms and (b) pore size distribu-
tion diagrams of bare CMK-3 and of Ni/CMK-3.
Hydrogenation of Carbonyl Compounds with Ni/CMK-3
In order to obtain an effective conversion of carbonyl com-
pounds into the corresponding alcohols, hydrogenation was
carried out using Ni/CMK-3 nanoparticles as a catalyst. Aceto-
phenone was chosen as a standard substrate to identify the
optimal reaction conditions (Table 1). Initially, we investigated
the effect of different hydrogen donors and bases on the
hydrogenation of acetophenone. For comparison purposes, iso-
propyl alcohol (IPA), 2-butanol, and 1-butanol were tested as a
hydrogen donor (Table 1, Entries 1–3). Among these com-
Figure 1. (a) TEM, (b) HAADF TEM, (c) magnified HAADF TEM image, (d–
f) scanning TEM image with elemental mapping (carbon, nickel, overlap), and
(g) XRD spectrum of Ni/CMK-3 catalyst. The bars (a, b) represent 100 nm.
Nitrogen adsorption isotherms were obtained to evaluate pounds, 2-butanol was found to be an effective hydrogen do-
the porous structure of CMK-3 and Ni/CMK-3 (Figure 2). Type-IV nor since it provided a high conversion of 89 %. The base also
isotherms were observed with hysteresis loops. The Brunauer– played a crucial role in the hydrogenation of acetophenone.
Emmett–Teller (BET) surface areas of bare CMK-3 and of Ni/ Both KOH (53 %) and KOtBu (74 %) were less active than NaOH
CMK-3 were calculated to be 1482.3 m2 g–1 and 1242.8 m2 g–1, (Table 1, Entries 2, 4–5). The conversion of the corresponding
respectively (Figure 2a). The total pore volume of the Ni/CMK-3 alcohols was greatly dependent on the reaction temperature. A
catalyst was 1.17 cm3 g–1, which was lower than that of the poorer conversion efficiency of 42 % was obtained at a low re-
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Table 1. Hydrogenation reactions of acetophenone with Ni/CMK-3.
Table 2. Hydrogenation reactions of various aromatic carbonyl compounds
with Ni/CMK-3.
Entry
Cat.
[mol-%]
Temp. Time
Base
Solvent
IPA
Conv.
[%][a]
[°C]
[h]
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
0.5
0.5
80
80
80
80
80
70
80
80
80
80
2
2
2
2
2
2
2
3
3
3
NaOH
NaOH 2-butanol
NaOH 1-butanol
68
89
4
53
74
42
84
95
92
75
KOH
2-butanol
KOtBu 2-butanol
NaOH 2-butanol
NaOH 2-butanol
NaOH 2-butanol
NaOH 2-butanol
NaOH 2-butanol
0.25
0.25
(Ni/AC)
0.25
(Ni/SBA-15)
10
11
80
3
NaOH 2-butanol
85
[a] Reaction conditions: acetophenone (1.0 mmol), base (2.0 mmol), solvent
(3.0 mL), determined by using GC–MS spectroscopy based on acetophenone.
action temperature of 70 °C (Table 1, Entry 6). The optimum
reaction conditions were found to be as follows: 0.25 mol-% Ni/
CMK-3 as catalyst, 2-butanol as the solvent, a temperature of
80 °C and a reaction time of 3 h (Table 1, Entry 9). In addition,
the Ni/CMK-3 catalyst showed a higher catalytic activity com-
pared to that of supported Ni/SBA-15 and Ni/activated carbon
(Ni/AC) (Table 1, Entries 10, 11). The synthesized Ni/SBA-15 and
Ni/AC catalysts showed much lower conversions of 85 % and
75 % than the 92 % of Ni/CMK-3 under the same reaction con-
ditions.
We extended the study on hydrogenation using the Ni/CMK-
3 catalyst to include a series of aromatic carbonyl compounds.
The Ni/CMK-3 catalyst showed high activities for the hydrogen-
ation of various aromatic carbonyl compounds under the opti-
mized reaction conditions, and the results are shown in Table 2.
Among the carbonyl compounds, benzaldehyde was converted
into benzyl alcohol within 0.5 h (Table 2, Entry 1). Using the
same amount of catalyst, the hydrogenation of aldehydes ex-
hibited higher activities as compared to that of ketones as the
carbonyl group of an aldehyde is more electrophilic and steri-
cally less hindered than that of ketones.
As the length of the carbon chain increased, the conversion
decreased. This was evidenced by the lower conversion ob-
served for propiophenone and butyrophenone as compared to
that of acetophenone (Table 2, Entries 2–3). In contrast, a high
conversion was obtained in the hydrogenation of benzo-
phenone under the optimized reaction conditions (Table 2, En-
try 4). We evaluated the effect of the acetophenone phenyl ring
substitution with electron-donating and electron-withdrawing
groups (Table 2, Entries 5, 8–11). Acetophenone substrates that
contained electron-donating groups in the para position
showed a lower conversion than those with electro-withdraw-
ing groups. In addition, substrates that were methylated at the
2′-, 3′- and 4′-positions were investigated for the influence of
position. 2′-Methylacetophenone exhibited a lower conversion.
[a] Reaction conditions: Ni/CMK-3 catalyst (1.47 mg), substrate (1.0 mmol),
NaOH (2.0 mmol), 2-butanol (3.0 mL), 80 °C, 3 h, determined by using GC–
MS spectroscopy based on substrate. [b] Reaction time 0.5 h.
ylacetophenone and 4′-methylacetophenone (Table 2, En-
tries 5–7). Hydrogenation of ketones with bulky substituents
was also carried out (Table 2, Entries 12–13). Only the reaction
involving 2-acetonaphthone gave the desired product in good
conversion.
Recyclability
Moving the substituent away from the reactive center did not The recyclability of the catalyst is one of the most important
affect the conversion greatly, as seen in the cases of 3′-meth- factors in a heterogeneous catalyst system. After the reaction,
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in the Ni/AC catalyst had chemical stability enough, even under
the basic reaction conditions, but its irregular and smaller pore
structure led to initial large and multiform Ni NPs (2–50 nm)
(Figure 5, c). Therefore, the activity of Ni/AC was seriously de-
creased after the first run. Furthermore, the initial particles that
are deposited on the activated carbon were easily aggregated
and formed larger particles (> 50 nm) after the catalytic reac-
tion (Figure 5, d).
Conclusions
An OMC support (CMK-3) with large surface area and high sta-
bility was prepared using SBA-15 as a silica template. The sur-
face area of bare Ni/CMK-3 was calculated to be 1242.8 m2 g–1.
The size of the small pores obtained in Ni/CMK-3 was found to
be ca. 6 nm. The Ni NPs clearly showed uniform dispersions,
and the average particle size was estimated to be 1.6 nm. The
Ni/CMK-3 catalyst showed an advantage in the hydrogenation
of carbonyl compounds and a higher catalytic activity com-
pared to those of other supported Ni/SBA-15 and Ni/AC cata-
lysts. Moreover, the stability of the catalyst was demonstrated
as there was no significant loss of catalytic activity, and the
structure of Ni/CMK-3 was unchanged in the hydrogenation of
acetophenone for six consecutive catalytic cycles.
Figure 3. Recyclability of Ni/CMK-3, Ni/SBA-15 and Ni/AC as a catalyst for the
hydrogenation of acetophenone. Reaction condition: Ni catalyst (0.5 mol-%),
acetophenone (5.0 mmol), NaOH (10.0 mmol), 2-butanol (15.0 mL), 80 °C, 3 h.
Figure 4. (a) TEM and (b) HADDF-TEM images of the recovered Ni/CMK-3
catalyst after reaction. All bars represent 50 nm.
Experimental Section
Chemicals: Pluronic P123 (Mw = 5800), tetraethyl orthosilicate
(TEOS, 98 %), nickel nitrate hexahydrate [Ni(NO3)2·6H2O, ACS rea-
gent, ≥ 98 %], sucrose, acetophenone, and 2-butanol were obtained
from Sigma–Aldrich. Activated carbon was purchased from Strem
Chemicals, Inc. Hydrochloric acid (HCl, 35 wt.-%) and sulfuric acid
(H2SO4, 95 %) were purchased from Junsei. The chemicals were
used as received without further purification.
Preparation of SBA-15 and CMK-3 Mesoporous Carbon: Mesopo-
rous silica SBA-15 was prepared by applying a hydrothermal
method reported in the literature.[33] Pluronic P123 (16.0 g), deion-
ized water (502.8 g) and HCl (97.2 g) were mixed in a 1 L polypropyl-
ene bottle. TEOS (34.0 g) was then added to the solution mixture
and aged at 40 °C for 24 h. After that, the reaction mixture was
transferred into a Teflon-lined autoclave and aged at 150 °C for
24 h. The suspension was precipitated by centrifugation. The pre-
cipitate was thoroughly washed with water and ethanol, and dried
in an oven at 60 °C for 6 h. The product was calcined in air at 550 °C
for 5 h to yield SBA-15 as a white powder. The CMK-3 mesoporous
carbon was replicated using SBA-15 as a silica template. SBA-15
(3.0 g) was added to the carbon precursor solution, which was ob-
tained by dissolving sucrose (4.1 g) and H2SO4 (0.5 g) in distilled
water (15 mL). The mixture was placed in an oven at 100 °C for 6 h
and subsequently aged at 160 °C for 2 h. After that, sucrose (2.5 g),
H2SO4 (0.3 g), and distilled water (15 mL) were added to the aged
mixture. The sample was carbonized at 800 °C and maintained un-
der an N2 flow (200 mL min–1) at that temperature for 2 h. Finally,
the carbon–silica composite was washed at room temperature with
Figure 5. TEM images of (a–b) the recovered Ni/SBA-15 catalyst after reaction,
(c) a fresh Ni/AC catalyst and (d) the recovered Ni/C after reaction. The bars
represent 200 nm (a, c, d) and 20 nm (b).
the Ni/CMK-3 catalyst was separated by centrifugation and re-
used for the next cycle under the same conditions. The results
showed no significant loss of catalytic activity for the hydrogen-
ation of acetophenone using Ni/CMK-3 for six consecutive cata-
lytic cycles (Figure 3). As shown in Figure 4, the structure of Ni/
CMK-3 remained unchanged upon completion of the reaction,
thus demonstrating the recyclability of the catalyst. However,
the recovered Ni/SBA-15 catalyst exhibited a loss of catalytic
activity from the fifth run (Figure 3), and we confirmed the
structure of the catalyst after recycling it six times. The original
2D hexagonal mesostructure of Ni/SBA-15 is totally collapsed
after the reaction by the used strong base NaOH, because silica
materials are not sufficiently stable under basic conditions (Fig-
hydrofluoric acid (2
M, 100 mL) to remove the silica template. The
product was filtered, washed with ethanol, and thermally treated
under an N2 flow (200 mL min–1) at 400 °C for 4 h.
Preparation of Ni/CMK-3, Ni/SBA-15, and Ni/AC Catalysts: To
ure 5, a–b).[29] Unlike SBA-15, the activated carbon support used prepare an Ni/CMK-3 catalyst, aqueous nickel nitrate solution (6.3
M,
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was performed by grinding the mixture under ambient conditions
for 10 min until the powder was homogeneously black. Next, the
mixed powder was placed in a polypropylene bottle and aged in
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General Procedure for the Hydrogenation Reactions of Aceto-
phenones to Alcohols: Ni/CMK-3 catalyst (1.47 mg), NaOH
(2.0 mmol), and 2-butanol (3.0 mL) were mixed and sonicated for
10 min. Next, the acetophenone (1.0 mmol) was added into the
mixture and vigorously stirred at 80 °C for 3 h. After the reaction,
the mixture was cooled to room temperature, and the catalyst was
separated by centrifugation. The separated catalyst was washed
several times with ethanol. Finally, the reaction products were ex-
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scopy.
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Acknowledgments
This research was supported by the Basic Science Research Pro-
gram through the National Research Foundation of Korea (NRF)
funded by the Ministry of Science, ICT & Future Planning (NRF-
2015R1D1A1A02060684 and NRF-2013R1A1A2012960). J. C. P.
thanks for the support funded by the Ministry of Trade, Industry
and Energy (MOTIE) of the Republic of Korea through project
no. 10050509. S. P. thanks for partial support by the >cgs>NRF
(2015R1D1A1A01058672) and a Korea Basic Science Institute re-
search grant (E36800).
Keywords: CMK-3 · Nickel · Nanoparticles · Hydrogenation ·
Mesoporous materials · Carbon · Heterogeneous catalysis
Received: March 21, 2016
Published Online: ■
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Nickel Nanoparticle Catalysts
Ni/CMK-3 was prepared by incorporat-
ing Ni particles formed inside the
pores of CMK-3 by impregnation of
D. Kim, H. Kang, H. Park, S. Park,
J. C. Park,* K. H. Park* ...................... 1–6
nickel
nitrate
and
subsequent
Nickel Nanoparticles Supported on
CMK-3 with Enhanced Catalytic Per-
formance for Hydrogenation of
Carbonyl Compounds
hydrogen reduction. The prepared Ni/
CMK-3 has a large surface area and a
very small nickel nanoparticle size
(1 nm) with the aim of achieving high
performance in catalytic hydrogen-
ation reactions.
DOI: 10.1002/ejic.201600318
Eur. J. Inorg. Chem. 0000, 0–0
www.eurjic.org
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