Conversion of succinic acid to 1,4-butanediol via dimethyl succinate over rhenium nano-catalyst supported on copper-containing mesoporous carbon

Article abstract of DOI:10.1166/jnn.2014.9943

Copper-containing mesoporous carbons (XCu-MC) with different copper content (X = 8.0, 12.7, 15.9, 23.3, and 26.8 wt%) were prepared by a single-step surfactant-templating method. Rhenium nano-catalysts supported on copper-containing mesoporous carbons (Re/XCu-MC) were then prepared by an incipient wetness method. Re/XCu-MC (X = 8.0, 12.7, 15.9, 23.3, and 26.8 wt%) catalysts were characterized by nitrogen adsorption-desorption isotherm, HR-TEM, FT-IR, and H₂- TPR analyses. Liquid-phase hydrogenation of succinic acid to 1,4-butanediol (BDO) via dimethyl succinate (DMS) was carried out over Re/XCu-MC catalysts in a batch reactor. The effect of copper content on the physicochemical properties and catalytic activities of Re/XCu-MC catalysts in the hydrogenation of succinic acid to BDO was investigated. Re/XCu-MC catalysts retained different physicochemical properties depending on copper content. In the hydrogenation of succinic acid to BDO, yield for BDO showed a volcano-shaped trend with respect to copper content. Thus, an optimal copper content was required to achieve maximum catalytic performance of Re/XCu-MC. It was also observed that yield for BDO increased with increasing the amount of hydrogen consumption by copper in the Re/XCu-MC catalysts.

Full text of DOI:10.1166/jnn.2014.9943

Article
Journal of
Nanoscience and Nanotechnology
Vol. 14, 8867–8872, 2014
Copyright © 2014 American Scientific Publishers
All rights reserved
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Printed in the United States of America
Conversion of Succinic Acid to 1,4-Butanediol via
Dimethyl Succinate Over Rhenium Nano-Catalyst
Supported on Copper-Containing Mesoporous Carbon
Ung Gi Hong, Jeong Kwon Kim, Joongwon Lee, Jong Kwon Lee, Jongheop Yi, and In Kyu Song∗
School of Chemical and Biological Engineering, Institute of Chemical Processes,
Seoul National University, Shinlim-Dong, Kwanak-Ku, Seoul 151-744, South Korea
Copper-containing mesoporous carbons (XCu-MC) with different copper content (X = 8ꢀ0, 12.7,
15.9, 23.3, and 26.8 wt%) were prepared by a single-step surfactant-templating method. Rhenium
nano-catalysts supported on copper-containing mesoporous carbons (Re/XCu-MC) were then pre-
pared by an incipient wetness method. Re/XCu-MC (X = 8ꢀ0, 12.7, 15.9, 23.3, and 26.8 wt%)
catalysts were characterized by nitrogen adsorption-desorption isotherm, HR-TEM, FT-IR, and H2-
TPR analyses. Liquid-phase hydrogenation of succinic acid to 1,4-butanediol (BDO) via dimethyl
succinate (DMS) was carried out over Re/XCu-MC catalysts in a batch reactor. The effect of copper
content on the physicochemical properties and catalytic activities of Re/XCu-MC catalysts in the
hydrogenation of succinic acid to BDO was investigated. Re/XCu-MC catalysts retained different
Delivered by Ingenta to: Nanyang Technological University
physicochemical properties depending on copper content. In the hydrogenation of succinic acid to
IP: 185.14.192.15 On: Sat, 11 Jun 2016 10:52:07
BDO, yield for BDO showed a volcano-shaped trend with respect to copper content. Thus, an opti-
Copyright: American Scientific Publishers
mal copper content was required to achieve maximum catalytic performance of Re/XCu-MC. It was
also observed that yield for BDO increased with increasing the amount of hydrogen consumption
by copper in the Re/XCu-MC catalysts.
Keywords: Mesoporous Carbon, Succinic Acid, 1,4-Butanediol, Copper Catalyst, Rhenium
Nano-Catalyst.
1. INTRODUCTION
activity for demethylation of DMS to BDO is also required
for efficient production of BDO from SA. Therefore, it is
important to find a suitable catalyst that has both methy-
lation activity (SA → DMS) and demethylation activity
(DMS → BDO) in the BDO production from SA. It has
also been reported that copper-based catalysts are efficient
for demethylation of DMS to BDO.11–13 Thus, a rhenium-
copper bimetal catalyst can be a potential candidate for the
production of BDO from SA.
1,4-Butanediol (BDO) is used as a desirable solvent in
plastic and elastic fiber industries.1ꢀ2 BDO is currently
produced from several feedstocks, such as maleic anhy-
dride, acetylene, and propylene oxide.3–5 However, these
petrochemical-based feedstocks have economical and envi-
ronmental problems.6 Therefore, demand for finding a
cheap and clean feedstock for the production of BDO has
continuously increased.
Mesoporous carbon has found successful applications as
a support due to its well-developed porosity and hydropho-
bic property.14 It has been reported that metal-containing
mesoporous carbon prepared by a single-step surfactant-
templating method can produce finely dispersed metal par-
ticles on the carbon surface.15 Therefore, it is expected
that copper-containing mesoporous carbon prepared by a
single-step surfactant-templating method can serve as a
catalyst and as a supporting material for rhenium at the
same time.
Recently, succinic acid (SA) has attracted much
attention as a cheap and bio-derived chemical that can be
converted into BDO.7ꢀ8 It has been reported that hydro-
genation of dicarboxylic acid with alcohol can yield diol
via alkyl oxalate.9 In the same manner, SA can react with
methanol to produce BDO via dimethyl succinate (DMS)
(Fig. 1). It is known that rhenium-based catalysts are effi-
cient for methylation of SA to DMS.10 However, strong
∗Author to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2014, Vol. 14, No. 11
1533-4880/2014/14/8867/006
doi:10.1166/jnn.2014.9943
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Hydrogenation of Succinic Acid
Hong et al.
5 wt% HF solution to remove silica template. The result-
ing copper-containing mesoporous carbon was denoted as
XCu-MC (X = 8ꢁ0, 12.7, 15.9, 23.3, and 26.8), where X
represented weight percentage of copper determined by
ICP-AES analysis. Rhenium nano-catalyst supported on
copper-containing mesoporous carbon (Re/XCu-MC) was
prepared by an incipient wetness impregnation method
using an acetone solution of rhenium chloride (ReCl5,
Aldrich). Rhenium loading was fixed at 5 wt% in all the cat-
alysts. The supported catalyst was calcined at 600 ꢀC, and it
was reduced with a mixed stream of hydrogen (2.5 ml/min)
and nitrogen (47.5 ml/min) at 600 ꢀC for 4 h prior to char-
acterization and catalytic reaction.
H2O
Succinic acid (SA)
MeOH
γ-Butyrolactone
Dimethyl succinate
(DMS)
(GBL)
H2
2.2. Characterization
Surface areas and pore volumes of supported rhenium cat-
alysts (Re/XCu-MC, X = 8ꢁ0, 12.7, 15.9, 23.3, and 26.8)
were calculated using the BET equation and the BJH
model, respectively, from nitrogen adsorption-desorption
measurements (ASAP2010, Micromeritics). Surface mor-
phologies of Re/XCu-MC catalysts were examined by
HR-TEM (Jeol, JEM-3000F) analysis. FT-IR spectra of
Re/XCu-MC catalysts were obtained with a Thermo
Nicolet 6700 spectrometer. The amount of hydrogen
consumption and reduction peak temperature of Re/XCu-
MC catalysts were examined by H2-TPR (temperature-
programmed reduction) experiments using a conventional
MeOH
1,4-Butanediol
(BDO)
Figure 1. Reaction pathways for the conversion of succinic acid (SA)
to 1,4-butanediol (BDO) via dimethyl succinate (DMS).
In this work, copper-containing mesoporous carbons
(XCu-MC) with different copper content (X = 8ꢁ0,
12.7, 15.9, 23.3, and 26.8 wt%) were prepared by a
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flow system equipped with a TCD (thermal conductivity
single-step surfactant-templating method. Rhenium nano-
IP: 185.14.192.15 On: Sat, 11 Jun 2016 10:52:07
ꢀ
detector) at temperatures ranging from 25 to 900 C with
catalysts supported on copper-containCinogpmyreisgohpto: rAomusecriacra- n Scientific Publishersꢀ
a ramping rate of 5 C/min. For the TPR measurements, a
bons (Re/XCu-MC) were then prepared by an incipient
wetness method. Re/XCu-MC catalysts were characterized
by nitrogen adsorption-desorption isotherm, HR-TEM, FT-
IR, and H2-TPR analyses. Liquid-phase hydrogenation of
succinic acid (SA) to 1,4-butanediol (BDO) was carried
out over Re/XCu-MC catalysts in a batch reactor. The
effect of copper content on the physicochemical proper-
ties and catalytic activities of Re/XCu-MC catalysts was
investigated.
mixed stream of H2 (2 ml/min) and N2 (20 ml/min) was
employed for 0.05 g of catalyst sample.
2.3. Hydrogenation of Succinic Acid
Liquid-phase hydrogenation of succinic acid (SA) to 1,4-
butanediol (BDO) was carried out over Re/XCu-MC cata-
lysts (X = 8ꢁ0, 12.7, 15.9, 23.3, and 26.8) in a batch reactor
at 200 ꢀC and 80 bar (H2). Succinic acid (0.5 g), methanol
(25 ml), and a reduced catalyst (0.2 g) were charged into
an autoclave (150 ml). 1,4-Dioxane (25 ml) was used as
a solvent for the reaction. The reactor was purged with
nitrogen to remove air, and it was then pressurized up to
40 bar using hydrogen. After heating the reactor to reac-
2. EXPERIMENTAL DETAILS
2.1. Preparation of Supported Rhenium
Catalysts (Re/XCu-MC)
Sucrose (Aldrich, 0.8 g), P123 (Aldrich, 1.6 g), and cop-
per nitrate (Aldrich, 0.1, 0.2, 0.3, 0.4, and 0.5 g) were dis-
solved in 4 M HCl solution (30 ml) at 40 ꢀC for 4 h under
stirring. After a silica precursor (TEOS, 3.6 ml, Aldrich)
was slowly added into the solution, the resultant was dried
overnight at 100 ꢀC. After filtering and washing the result-
ing precipitate with de-ionized water, it was dried at 80 ꢀC
to obtain a sucrose/copper/surfactant/silica composite. The
2 g of composite was treated with 40 ml of 0.4 M H2SO4
solution for 12 h. After drying the mixture at 160 C for
8 h, the obtained brown solid was carbonized at 800 C
for 4 h at a heating rate of 5 C/min in a nitrogen stream
(100 ml/min). The solid product was further treated with
ꢀ
tion temperature (200 C), hydrogen pressure was raised
up to 80 bar. The catalytic reaction was carried out for
20 h. The reaction mixture was stirred at 700 rpm in order
to avoid mass transfer limitation. Reaction products were
analyzed using a gas chromatograph (Younglin, ACME-
6100) equipped with a FID (flame ionization detector).
3. RESULTS AND DISCUSSION
3.1. Morphology and FT-IR Studies of Supported
Rhenium Catalysts (Re/XCu-MC)
HR-TEM images of Re/XCu-MC catalysts (X = 8ꢁ0, 12.7,
15.9, 23.3, and 26.8) reduced at 600 ꢀC are shown in
ꢀ
ꢀ
ꢀ
8868
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Hong et al.
Hydrogenation of Succinic Acid
(a) Re/8.0Cu-MC
(b) Re/12.7Cu-MC
1639 cm–1 1352 cm–1
(C=O) (–OH)
967 cm–1
(C–O–C)
Re/8.0Cu-MC
Re/12.7Cu-MC
20 nm
20 nm
Re/15.9Cu-MC
Re/23.3Cu-MC
(c) Re/15.9Cu-MC
(d) Re/23.3Cu-MC
Re/26.8Cu-MC
20 nm
20 nm
2000
1800
1600
1400
1200
1000
800
(e)
Re/26.8Cu-MC
Wavenumber (cm-1)
Figure 3. FT-IR spectra of supported rhenium catalysts (Re/XCu-MC)
reduced at 600 ꢀC.
(X = 8ꢁ0, 12.7, and 15.9) catalysts containing C
O
C
bond retained an ordered pore structure and fine metal
20 nm
dispersion. However, an excess amount of copper in the
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Re/23.3Cu-MC and Re/26.8Cu-MC prohibited the for-
Figure 2. HR-TEM images of supported rhenium catalysts (Re/XCu-
IP: 185.14.192.15 On: Sat, 11 Jun 2016 10:52:07
mation of C C bond and suppressed the forma-
O
MC) reduced at 600 ꢀC.
Copyright: American Scientific Publishers
tion of ordered copper-carbon structure, leading to large
metal aggregation and pore blocking. Thus, TEM and FT-
IR results revealed that an optimal copper content was
required to obtain ordered mesoporous structure and fine
metal dispersion of the catalysts.
Figure 2. Re/XCu-MC (X = 8ꢁ0, 12.7, and 15.9) catalysts
retained a 2-dimensional ordered carbon nanorod array,
while Re/XCu-MC (X = 23ꢁ3 and 26.8) catalysts had a
collapsed carbon structure. As a consequence, Re/XCu-
MC (X = 8ꢁ0, 12.7, and 15.9) catalysts retained finely
dispersed small metal particles (less than 10 nm), while
Re/XCu-MC (X = 23ꢁ3 and 26.8) catalysts had large metal
aggregates (more than 15 nm).
3.2. Physicochemical Properties of Supported
Rhenium Catalysts (Re/XCu-MC)
Nitrogen adsorption–desorption isotherms and textural
properties of Re/XCu-MC catalysts (X = 8ꢁ0, 12.7, 15.9,
Figure 3 shows the FT-IR spectra of Re/XCu-MC cata-
ꢀ
lysts reduced at 600 C. Re/XCu-MC (X = 8ꢁ0, 12.7, and
Re/8.0Cu-MC
15.9) showed three characteristic IR bands at 967 cm−1
0.15
Re/12.7Cu-MC
(C
O
C), 1352 cm−1 (–OH), and 1639 cm−1 (C O),
0.10
Re/15.9Cu-MC
while Re/XCu-MC (X = 23ꢁ3 and 26.8) catalysts showed
only two characteristic IR bands at 1352 cm−1 (–OH)
and 1639 cm−1 (C O). Because copper nanoparticles
tend to aggregate, it is important to form an interaction
between copper and carbon for fine dispersion of copper
in the copper-carbon composite material. It is believed that
Re/15.9Cu-MC
0.05
0.00
0
5
10
15
20
25
Pore size (nm)
Re/23.3Cu-MC
Re/26.8Cu-MC
C
O
C bond on the surface of carbon nanorods played
an important role in overcoming Van der Waal’s force
between carbons,16 leading to a strong interaction between
copper precursor and carbon atoms during the prepara-
0.0
0.2
0.4
0.6
0.8
1.0
Relative pressure (P/P0)
tion step. In other words, the presence of C
O
C bond
gives rise to the well incorporation of copper into carbon
framework in the Cu-MC support. Therefore, Re/XCu-MC
Figure 4. Nitrogen adsorption-desorption isotherms of supported rhe-
nium catalysts (Re/XCu-MC) reduced at 600 ꢀC.
J. Nanosci. Nanotechnol. 14, 8867–8872, 2014
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Hydrogenation of Succinic Acid
Hong et al.
Table I. Physicochemical properties of Re/XCu-MC catalysts.
Surface area
(m2/g-cat.)
Pore volume
(cm3/g-cat.)
Average pore
size (nm)
Amount of hydrogen consumption
by rhenium (mmol/g-cat.)
Amount of hydrogen consumption
by copper (mmol/g-cat.)
Re/8.0Cu-MC
Re/12.7Cu-MC
Re/15.9Cu-MC
Re/23.3Cu-MC
Re/26.8Cu-MC
865
840
771
412
339
1.26
1.30
1.17
0.61
0.33
5.5
5.5
5.5
5.2
3.9
7.9
7.4
7.0
6.2
4.1
5ꢁ4
16ꢁ8
25ꢁ1
4ꢁ2
2ꢁ3
23.3, and 26.8) are presented in Figure 4 and Table I,
respectively. All the Re/XCu-MC catalysts exhibited type-
IV isotherms. With decreasing copper content, more appar-
ent type-H3 hysteresis loop indicating the existence of
mesopores was developed.17 Surface area of Re/XCu-MC
catalysts decreased with increasing copper content. Aver-
age pore size of Re/XCu-MC catalysts was in the meso-
pore range (3.9–5.5 nm). Re/XCu-MC (X = 8ꢁ0, 12.7, and
15.9) catalysts retained high surface area (865, 840, and
771 m2/g, respectively) and large pore volume (1.26, 1.30,
and 1.17 cm3/g, respectively), while Re/XCu-MC (X =
23ꢁ3 and 26.8) catalysts had low surface area (412 and
339 m2/g, respectively) and small pore volume (0.61 and
0.33 cm3/g, respectively). These results indicate that cop-
per in the Re/XCu-MC (X = 8ꢁ0, 12.7, and 15.9) catalysts
was well incorporated into carbon framework, resulting in
high surface area and large pore volume. As described ear-
amount of hydrogen consumption by rhenium (calculated
from TPR peak area) in the Re/XCu-MC (X = 8ꢁ0, 12.7,
15.9, 23.3, and 26.8) catalysts decreased with increasing
copper content due to the decrease of metal dispersion.
It was observed that the amount of hydrogen consump-
tion by copper increased with increasing copper content in
the Re/XCu-MC (X = 8ꢁ0, 12.7, and 15.9) catalysts. How-
ever, the amount of hydrogen consumption by copper in
the Re/XCu-MC (X = 23ꢁ3 and 26.8) was much smaller
than that in the Re/XCu-MC (X = 8ꢁ0, 12.7, and 15.9)
due to the copper aggregation. From Table I, it should be
noted that the amount of hydrogen consumption by cop-
per in the Re/XCu-MC (X = 8ꢁ0, 12.7, 15.9, 23.3, and
26.8) showed a volcano-shaped trend with respect to cop-
per content. The above results indicate that physicochemi-
cal properties could be controlled by changing the amount
of copper content in the Re/XCu-MC catalysts.
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lier, however, an excess amount of copper in the Re/XCu-
IP: 185.14.192.15 On: Sat, 11 Jun 2016 10:52:07
MC (X = 23ꢁ3 and 26.8) catalysts did not cause a strong
3.3. Hydrogenation of Succinic Acid to 1,4-Butanediol
(BDO) Over Supported Rhenium
Copyright: American Scientific Publishers
interaction between copper and carbon framework during
the preparation step, leading to the pore blocking by cop-
per aggregation.
Nano-Catalysts (Re/XCu-MC)
Catalytic activities of Re/XCu-MC catalysts (X = 8ꢁ0,
12.7, 15.9, 23.3, and 26.8) in the liquid-phase hydrogena-
tion of succinic acid (SA) are summarized in Table II.
1,4-Butanediol (BDO) was produced as a target prod-
uct and dimethyl succinate (DMS) was produced as
TPR results of Re/XCu-MC (X = 8ꢁ0, 12.7, 15.9, 23.3,
and 26.8) catalysts are presented in Figure 5 and Table I.
TPR profiles of Re/XCu-MC (X = 8ꢁ0, 12.7, 15.9, 23.3,
and 26.8) catalysts revealed that there were two hydro-
gen consumption peaks (reduction peaks) appearing at
ꢀ
ꢀ
270–310 C and 450–600 C, which were attributed to
the reduction of rhenium and copper species, respectively.
Reduction peak temperature of rhenium in the Re/XCu-
MC (X = 8ꢁ0, 12.7, 15.9, 23.3, and 26.8) catalysts showed
a slight difference. However, reduction temperature of cop-
per in the Re/XCu-MC (X = 8ꢁ0, 12.7, and 15.9) catalysts
significantly increased with increasing copper content. It
has been reported that single-step self assembly synthe-
sis of binary materials caused a strong interaction dur-
ing the preparation step.18 Therefore, it is believed that
the interaction between copper species and carbon frame-
work in the XCu-MC (X = 8ꢁ0, 12.7, and 15.9) increased
with increasing copper content, leading to an increased
reduction temperature of copper with increasing copper
content. On the other hand, although large amount of cop-
per included, Re/XCu-MC (X = 23ꢁ3 and 26.8) showed
278
508
Re/8.0Cu-MC
283
577
Re/12.7Cu-MC
591
301
Re/15.9Cu-MC
297
498
Re/23.3Cu-MC
278
452
Re/26.8Cu-MC
0
100 200 300 400 500 600 700 800 900
Temperature (ºC)
ꢀ
ꢀ
low reduction temperature of copper (498 C and 452 C,
respectively) due to a weak interaction between carbon
species and copper aggregation. As listed in Table I, the
Figure 5. TPR profiles of supported rhenium catalysts (Re/XCu-MC)
calcined at 600 ꢀC.
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Hong et al.
Hydrogenation of Succinic Acid
Table II. Catalytic performance of Re/XCu-MC catalysts in the liquid-
phase hydrogenation of succinic acid (reaction temperature = 200 ꢀC,
reaction pressure = 80 bar, reaction time = 20 h).
In order to investigate the effect of hydrogen consump-
tion by copper in the Re/XCu-MC (X = 8ꢁ0, 12.7, 15.9,
23.3, and 26.8) catalysts on the catalytic activity in the
hydrogenation of SA, a correlation between the amount of
hydrogen consumption by copper in the Re/XCu-MC cat-
alysts and yield for BDO was established. Figure 6 shows
the correlation between the amount of hydrogen consump-
tion by copper and yield for BDO in the hydrogenation
of SA. The correlation clearly shows that yield for BDO
increased with increasing the amount of hydrogen con-
sumption by copper. This result strongly supports that the
capacity of hydrogen consumption by copper served as a
key factor determining the catalytic activity in the hydro-
genation of SA to BDO over Re/XCu-MC catalysts.
Yield (%)
Conversion of SA (%)
BDO
DMS
GBL
Re/8.0Cu-MC
Re/12.7Cu-MC
Re/15.9Cu-MC
Re/23.3Cu-MC
Re/26.8Cu-MC
100
100
100
100
100
6ꢁ2
7ꢁ7
11ꢁ3
5ꢁ7
83.6
79.8
65.4
86.3
91.1
10ꢁ2
12ꢁ5
23ꢁ3
8ꢁ0
4ꢁ2
4ꢁ6
an intermediate via methylation of SA with methanol.
Cyclization of SA and DMS by rhenium component of
the catalysts produced ꢂ-butyrolactone (GBL) as a by-
product as shown in Figure 1. All the catalysts exhib-
ited a complete conversion (100%) of SA. This means
that the catalytic function of rhenium was sufficient
in the liquid-phase hydrogenation of SA to DMS over
Re/XCu-MC catalysts. However, yield for BDO showed
a volcano-shaped trend with respect to copper content.
This means that an optimal copper content was required
for maximum catalytic performance. Among the catalyst
tested, Re/15.9Cu-MC catalyst showed the highest yield
for BDO (11.3%). The enhanced catalytic performance
of Re/15.9Cu-MC might be due to the largest amount of
hydrogen consumption by copper. It has been reported that
4. CONCLUSIONS
Copper-containing mesoporous carbons (XCu-MC) with
different copper content (X = 8ꢁ0, 12.7, 15.9, 23.3, and
26.8 wt%) were prepared by a single-step surfactant-
templating method. Rhenium nano-catalysts supported on
copper-containing mesoporous carbons (Re/XCu-MC, X =
8ꢁ0, 12.7, 15.9, 23.3, and 26.8) were then prepared by an
incipient wetness method. Physicochemical properties of
Re/XCu-MC (X = 8ꢁ0, 12.7, 15.9, 23.3, and 26.8 wt%)
were affected by copper content. The amount of hydro-
gen consumption by copper in the Re/XCu-MC (X = 8ꢁ0,
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12.7, 15.9, 23.3, and 26.8) showed a volcano-shaped trend
hydrogen consumption by metal for reduction plays an
IP: 185.14.192.15 On: Sat, 11 Jun 2016 10:52:07
with respect to copper content. In the liquid-phase hydro-
genation of SA to BDO, yield for BDO also showed a
volcano-shaped trend with respect to copper content. Yield
for BDO increased with increasing the amount of hydro-
gen consumption by copper in the Re/XCu-MC catalysts.
It is concluded that an optimal copper content was required
to achieve maximum catalytic performance of Re/XCu-
MC catalysts in the hydrogenation of SA to BDO.
Copyright: American Scientific Publishers
important role in determining the catalytic performance in
the liquid-phase hydrogenation of succinic acid.18 It has
also been reported that dealkylation of alkyl oxalate is a
rate-determining step in the hydrogenation of dicarboxylic
acid with alcohol.19 Therefore, it is believed that the excel-
lent catalytic performance of Re/15.9Cu-MC catalyst was
due to the largest amount of hydrogen consumption by
copper and the enhanced demethylation activity of copper
from DMS to BDO.
Acknowledgments: This subject is supported by Korea
Ministry of Environment as “Converging Technology
Project (202-091-001).”
12
Re/15.9Cu-MC
10
8
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Received: 27 February 2013. Accepted: 18 February 2014.
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Copyright: American Scientific Publishers
8872
J. Nanosci. Nanotechnol. 14, 8867–8872, 2014