Bimetal modified ordered mesoporous carbon as a support of Rh catalyst for ethanol synthesis from syngas

Article abstract of DOI:10.1016/j.catcom.2011.12.015

Ordered mesoporous carbons (OMCs) containing highly dispersed iron and manganese bimetal particles have been synthesized by an organic-organic self-assembly method. The characterization results showed that the ordered mesostructure of carbons still remained after the incorporation of bimetal particles into the carbon matrix. These materials were used as supports of Rh based catalysts for ethanol synthesis from CO hydrogenation reaction. The catalysts supported on the metal modified OMC exhibited much better activity and selectivity than that supported on the OMC without modified metal particles and conventional catalysts supported on silica.

Full text of DOI:10.1016/j.catcom.2011.12.015

Catalysis Communications 19 (2012) 100–104
Contents lists available at SciVerse ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Bimetal modified ordered mesoporous carbon as a support of Rh catalyst for ethanol
synthesis from syngas
a,c
a,b,
⁎, Weimiao Chen , Wenda Dong a,c, Yanpeng Pei a,c, Juan Zang a,c
a
Xiangen Song , aYunjie Ding
,
a
Li Yan , Yuan Lu
a
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Science, China
Graduate School of Chinese Academy of Science, Chinese Academy of Science, Beijing 100039, China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 7 October 2011
Received in revised form 8 December 2011
Accepted 11 December 2011
Available online 20 December 2011
Ordered mesoporous carbons (OMCs) containing highly dispersed iron and manganese bimetal particles
have been synthesized by an organic–organic self-assembly method. The characterization results showed
that the ordered mesostructure of carbons still remained after the incorporation of bimetal particles into
the carbon matrix. These materials were used as supports of Rh based catalysts for ethanol synthesis from
CO hydrogenation reaction. The catalysts supported on the metal modified OMC exhibited much better activ-
ity and selectivity than that supported on the OMC without modified metal particles and conventional cata-
lysts supported on silica.
Keywords:
Ordered mesoporous carbon
Bimetal modified
CO hydrogenation
Ethanol synthesis
Rh
© 2011 Elsevier B.V. All rights reserved.
1
. Introduction
Ordered mesoporous carbons (OMCs) have stimulated extensive
based ethylene [12]. Owing to rising prices of crude oil and global
foodstuff crisis, the two processes become unattractive for large
scale production of ethanol. The conversion of syngas (a mixture of
CO and H ) reformed from coal, natural gas, and biomass may be a
interest due to their specific properties. Among them, the metal mod-
ified ordered mesoporous carbons (MMOMCs) have been thoroughly
studied owing to their various applications such as catalysts [1], sep-
arations [2], and fuel cell [3]. There are mainly two routes for intro-
ducing the metal nanoparticles into the mesoporous carbon matrix.
One method is called hard template. The main steps are as follows:
firstly, dispersing the desired metal into the pore wall of silica then
filling mesopore of silica with appropriate carbon source, followed
by carbonization and removal of silica template [4–7]. Another way
is simple, and highly effective to incorporate the metal species into
the mesoporous carbon wall. This approach involves introduction of
the metal precursor into the reaction mixture composed of a surfac-
tant and an oligomer of phenolic resin. The metal particles will be dis-
persed throughout the mesoporous carbon framework after removal
of surfactant and carbonation. Through this route, the MMOMCs con-
taining TiC [8], MoC [9], Ir [10], and Fe [11] nanoparticles have been
synthesized recently.
2
promising alternative route for the ethanol production. After exten-
sive research efforts in the last decades, it was found that the Rh
based catalysts promoted by Fe [13–15], Mn [16–18], and bimetal
[19–21] exhibited accessible activity and selectivity for the ethanol
synthesis from syngas. CO hydrogenation over Rh based catalyst is
very sensitive to the structure of active Rh sites and CO conversion
and oxygenates selectivities vary as a function of Rh particle size
[22–24]. Sugi and coworkers [25] pointed out the optimum particle
size of Rh cluster for C2 oxygenates synthesis was about 3–4 nm.
Bao et al. found that the ethanol production was enhanced greatly
when the active metal nanoparticles were confined inside carbon
nanotubes (CNTs) [26]. They also investigated the carrier effects of
different carbonaceous materials and suggested that the synergetic
effect of nanochannels and graphitic-like structure might also greatly
affect the activity and selectivity [27]. This synergetic confinement
effect related to CNTs may be applied to the MMOMCs because they
both have something in common such as uniform pore size, and similar
graphitic structure of carbon [28,29].
As a green, sustainable fuel additive, ethanol is attracting more
and more attention in recent years. Currently, ethanol is produced
primarily by fermentation of sugars and hydration of petroleum-
Although the MMOMCs containing many different metal nanopar-
ticles have been synthesized, the metals embedded into the mesopor-
ous carbon matrix reported before are all single metal, almost no
bimetals or trimetals. Therefore, it is a challenge to incorporate two
or more metals into the mesoporous carbon and find their
⁎
Corresponding author. Tel.: +86 411 84379143; fax: +86 411 84379143.
E-mail address: dyj@dicp.ac.cn (Y. Ding).
1566-7367/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2011.12.015

X. Song et al. / Catalysis Communications 19 (2012) 100–104
101
applications in some fields. Herein, we will report for the first time a
facile method to synthesize highly ordered mesoporous carbon mod-
ified by Mn and Fe bimetal under an acidic medium, and then explore
their catalytic properties as a support of Rh catalyst for ethanol syn-
thesis from syngas.
subsequently analyzed on-line by Agilent 3000A Micro GC with TCD
detector. The produced oxygenates completely dissolved in de-
ionized water were analyzed off-line by Varian 3800 GC with FID
detector, using n-pentanol as an internal standard. The syngas con-
version and product selectivity were calculated according to the fol-
lowing equations:
2
. Experimental section
∑
niMi
MCO
niMi
CO conversion ½%ꢀ ¼
where n
ꢁ 100; Selectivity ½%ꢀ ¼
ꢁ 100
i
2
.1. Preparation of catalysts
∑ n M
i
The detailed steps of bimetal modified OMC synthesis route dem-
i
is the number of carbon atoms in product i, M
i
is the total
onstrate as follows: 12.5 g F127 (Triblock poly (ethylene oxide)-b-
poly (propylene oxide)-b-poly (ethylene oxide) copolymer Pluronic
F127) and 16.5 g resorcinol were together dissolved in a 100 g mix-
ture of water/ethanol (50/50 vol.%) under stirring at room tempera-
mole number of product i during a certain reaction time, and MCO is
the total mole number of carbon monoxide in the feed during a certain
reaction time.
ture, then 7.5 g hydrated manganese nitrate (Mn(NO
3
)
2 2
·4H O) and
3. Results and discussion
1
.5 g hydrated iron nitrate (Fe(NO ·9H O) were added into the
3
)
3
2
mixture. When a uniform solution formed after about half an hour
continuous stirring, 12.5 g formaldehyde (37 wt.%) was dropped
into the solution in 30 min. After adjusting the pH value to 0.8 and
3.1. Characterization
In the low-angle XRD spectra (Fig. 1 insets), the diffraction peak at
2θ range of 0.5–1° can be observed from the curves of all the samples,
which proves the existence of 2-D hexagonally ordered mesostruc-
ture. The quite close peak intensity of these four samples suggests
that the incorporation of metal particles hardly destroy the ordered
mesostructure of the samples. The wide-angle XRD patterns of all
samples exhibit two broad diffraction peaks centered at 22.5° and
43.5°, which are in accordance with an amorphous carbon framework
[9]. In the case of FeOMC sample, a distinguishable diffraction peak at
1
.0 using HCl (37 wt.%), the mixture was kept standing until it
began to separate into two layers. Further aging for 60 h, the upper
layer was discarded. The lower layer was mechanically stirred over-
night and the formed material was further thermal polymerized at
1
3
3
00 °C for 48 h. Finally, the template agent was decomposed at
50 °C for 3 h and the phenolic resin was carbonized at 850 °C for
h under an argon atmosphere. The resulted composite was desig-
nated as MnFeOMC. For comparison, some single metal modified
OMCs and a pure OMC were synthesized by the same method and
designated as MnOMC, FeOMC and OMC respectively.
The catalysts were prepared by impregnation method with etha-
nol solution of the precursor. The detailed steps are as follows: The
Rh loading of all the catalysts was 2.0 wt.%. The MnFeOMC sample
2 3
35.8° can be assigned to the (311) diffraction of γ-Fe O (JCPDS 00-
039-1346). The weak intensity of the peak may be caused by the
low content (Table 1) and the high dispersion of Fe species. An inten-
sive diffraction peak at 2θ=34.9°, along with three resolved diffrac-
tion peaks at 2θ=40.5°, 58.6°, and 70.1° can be observed in the
XRD pattern of MnOMC sample, which can be indexed as the (111),
(200), (220), and (311) diffraction of cubic MnO (JCPDS 01-075-
1090), respectively.
The XRD pattern of MnFeOMC sample possesses some new char-
acteristics. Firstly, a narrow peak located at 26.47° which is a charac-
teristic peak of graphite-like carbon superimposes on a broad profile
[4]. This suggests that MnFeOMC composite contains a small quantity
of graphitized carbon. It is well known that certain metal nanoparti-
cles such as Fe, Co, Ni, and Mn can catalyze the conversion of amor-
phous carbon toward graphitic carbon at high temperature in an
inert gas atmosphere [28,29]. Secondly, the original weak resolved
was impregnated with RhCl
3
solution. The MnOMC support was im-
solution
pregnated with RhCl solution and different amounts of FeCl
3
3
to explore the optimum Fe loading on the RhFe/MnOMC catalysts. The
same method was used to optimize the Mn loading on the RhMn/
FeOMC catalysts. Besides RhCl solution, the OMC support was im-
3
pregnated with Mn and Fe solution with their optimum loading.
The impregnated catalysts were further dried at 120 °C overnight.
The catalysts were separately denoted as Rh/MnFeOMC, RhFe/
MnOMC, RhMn/FeOMC and RhMnFe/OMC.
2
.2. Characterization
2 3
peak belonging toγ-Fe O disappeared. Thirdly, compared with the
Powder X-ray diffraction (XRD) patterns were recorded with a
MnOMC sample, almost all the diffraction peaks of manganese spe-
cies shift right about 0.3°, indicating that a new species has formed
PANalytical X'Pert-Pro powder X-ray diffractometer using Cu Kα radi-
ation (λ=0.15418 nm), operated at 40 kV and 150 mA. Transmission
electron microscopy (TEM) images were taken on a JEOL2000 EX
electronic microscope with an accelerating voltage of 120 kV, while
high resolution transmission electron microscopy (HRTEM) was per-
(a)
(b)
2
formed on a Tecnai G F30 S-Twin transmission electron microscopy
(
c)
(
d)
2
operating at 300 kV. N adsorption–desorption isotherms were mea-
1
2
3
sured by a Micromeritics ASAP-2010 at 77 K. TPR and CO chemisorp-
tion experiments were performed on a Micromeritics Autochem 2910
apparatus. The metal contents were determined by inductively
coupled plasma (ICP) on an IRIS Intrepid II XPS instrument. Before
ICP measurements, the samples were calcined at 600 °C for 6 h, then
dissolved by nitric acid.
(d)
(c)
2 theta (degree)
(b)
(a)
2
.3. Catalytic activation and test
1
0
20
30
40
50
60
70
80
CO hydrogenation was carried out in a fixed bed micro-reactor
2
theta (degree)
−
1
under 573 K, 5.0 MPa (H
2
/CO=2) and GHSV=12,000 h . Before
flow at
23 K for 1.5 h. The effluent passed through a condenser and
the reaction, the catalysts were reduced in situ in a pure H
2
Fig. 1. Low-angle (inset) and wide-angle XRD patters of (a) OMC, (b) FeOMC, (c) MnOMC,
and (d). MnFeOM.
6

102
X. Song et al. / Catalysis Communications 19 (2012) 100–104
Table 1
2 3
plane of cubic γ-Fe O and the [200] plane of cubic Fe0.099Mn0.901O.
Textural property of the four samples.
We believe that the embedded structure can avoid metallic particles
aggregation in some level due to the growth restriction caused by
the nanopore.
Sample
S
BETa/
2
V
M
b/
V
T
c/
D
(nm)
P
d/
Mn content
(wt.%)
Fe content
(wt.%)
3
3
e
e
(
m /g)
(cm /g)
(cm /g)
OMC
743
683
675
664
0.15
0.12
0.12
0.12
0.75
0.65
0.63
0.62
5.2
4.9
4.9
4.9
0.0
2.45
0.0
0.0
0.0
0.35
0.25
MnOMC
FeOMC
MnFeOMC
3.2. Catalytic activity
2.26
In order to further study the catalytic properties of the fabricated
materials, we used them as the supports of Rh based catalysts for
the ethanol synthesis from syngas. The performance of CO hydroge-
nation over the catalysts was summarized in Table 2. It was found
that the CO conversion and ethanol selectivity of catalyst supported
on the metal modified OMC were significantly improved, particularly
in the case of the Rh/MnFeOMC sample. The CO conversion and etha-
nol selectivity of the Rh/MnFeOMC catalyst increased about 8 times
and 1.5 times respectively by contrast with those of the RhMnFe/
a
Brunauer–Emmet–Teller (BET) surface area.
Micropore volume determined by t-plot.
b
c
Total pore volume calculated from the amount of nitrogen adsorbed at a relative
) of 0.99.
pressure (p/p
0
d
Pore diameter calculated by the Barrett–Joyner–Halenda (BJH) method using
desorption branches.
e
The metal contents were analyzed by ICP method.
when manganese and iron bimetals were together introduced into
the OMC material. The four peaks can be respectively indexed as
4
OMC catalyst, while the selectivity for the main by-product CH de-
creased from 41% to 30%. Compared with sample supported on bimet-
al modified OMC, the activity and ethanol selectivity of catalysts
supported on the single metal modified OMCs decreased a little, but
still far exceeded those of the catalyst supported on pure OMC. Com-
pared with previously reported similar recipe catalyst supported on
silica, the catalysts supported on the MMOMCs still exihibited better
activity and higher ethanol selectivity under the similar reaction con-
ditions (Table 2). The performance of CO hydrogenation was strongly
influenced by the presence of promoters [30]. A strong interaction be-
tween the active promoters and the Rh particles creates tilted adsorp-
(
111), (200), (220), and (311) diffraction of cubic iron manganese
oxide (Fe0.099Mn0.901O) (JCPDS 01-077-2362). The chemical formula
of iron manganese oxide (Fe0.099Mn0.901O) was also consistent with
the element analysis result.
Nitrogen sorption isotherms of the four samples show representa-
1
tive type IV curves with an obvious H -type hysteresis loops (Fig. 2),
indicating the mesoporous structure of the materials. Clear capillary
condensation is observed between the relative pressures P/
P
0
=0.5–0.8 corresponding to a narrow and uniform pore distribu-
tion, which could be observed from the pore size distribution curves
Fig. 2 inset) calculated by BJH method based on the desorption
0
+
n+
tion mode of CO, which can be described as (Rh
x
Rh
y
)–O–M
where
n+
(
a part of Rh atom which have intimate contact with promoter (M
exists as Rh [31]. A tilted adsorption of CO facilitates the dissociation
of CO to form an adsorbed \CH \ species. Furthermore, it is believed
that Rh was more active for undissociated CO insertion than Rh to
form C oxygenates [32].
In Fig. 4, The twoTPR peaks of FeOMC sample may be induced by
the reduction from Fe to FeO and FeO to Fe. The first TPR peak of
)
+
branch. The average pore size of MMOMCs becomes a little small
due to the incorporation of metal particles and the BET surface area
also slightly reduced (see Table 1).
TEM images of the samples clearly show large domains of ordered
stripe-like and hexagonally arranged patterns (Fig. 3), which are con-
sistent with the analysis of the low-angle XRD patterns. From TEM
images of the OMC sample (Fig. 3a), parallel channels with pore size
of about 5 nm and pore wall thickness of ca. 7 nm can be observed.
It can be noticed that the nanoparticles (the dark spots) about
x
+
0
2
2 3
O
MnOMC sample reflected the reduction of MnO. The first peak of
MnFeOMC sample which located bentween the first peak of FeOMC
sample and that of MnOMC sample should be attributed to the reduc-
tion of Fe0.099Mn0.901O. By contrast with the FeOMC, MnOMC, and
MnFeOMC three carriers, most corresponding peaks of their Rh cata-
lysts shift toward low temperature, the shift suggests the intimate
contact between the embedded metal nanoparticles and Rh particles.
In the cases of RhMnFe/OMC, RhMn/FeOMC, and RhFe/MnOMC cata-
lysts, the interaction between metals can exist in various modes,
such as Rh and Mn, Rh and Fe, Mn and Fe, Rh and Mn and Fe. On
the TPR patterns of the above three catalysts, the first peak could be
6–14 nm are highly dispersed and dominantly imbedded in the car-
bon walls although some of the large particles can penetrate the
pore walls through the mesochannels. Moreover, from the HRTEM
images (Fig. 3e, f), one can clearly see the lattice fringes with d spac-
ing of 2.52 Å and 2.22 Å, which correspond respectively to the [311]
5
4
4
3
3
2
2
1
00
50
00
50
00
50
00
3+
3
3
.5
.0
attributed to the reduction of Rh . While in the case of Rh/
OMC
MnFeOMC catalyst, due to the only interaction between Rh and iron
manganese oxide particles, the original low reduction temperature
peak of Rh and the high temperature of iron manganese oxide over-
lapped in the middle. Because of the intimate contact, the embedded
metal oxide nanoparticles can hinder the reduction of Rh ion. Thus,
MnOMC
FeOMC
MnFeOMC
2.5
2
1
1
0
.0
.5
.0
.5
0
+
n+
more formation of the (Rh
tion facilitates the more CO activation and more insertion into
adsorbed \CH \ species. From Table 2, we can observe that the
CO selectivity of the catalysts supported on the MMOMCs was obvi-
x
Rh
y
)–O–M
active sites during reduc-
0.0
2
4
6
8
10
12
Pore diameter(nm)
x
OMC
2
MnOMC
FeOMC
MnFeOMC
ously higher than that of the catalyst supported on the pure OMC.
This indicates the embedded metal particles could promote the
water–gas shift reaction which would produce a partial higher con-
2
centration of H inside the nanochannel of MMOMCs and will further
accelerate the hydrogenation of acetaldehyde and acetic acid. Accord-
ingly, the CO conversion and ethanol selectivity can be greatly in-
creased. In addition, the pore size distribution of MMOMCs channels
concentrates at 3–6 nm, which is the optimum size of Rh particles
50
0
.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure (P/P0)
2
to form C oxygenates. And the Rh particle sizes are calculated
Fig. 2. Nitrogen sorption isotherms and pore size distributions (inset) of OMC, MnOMC,
FeOMC, and MnFeOMC.
about 2.4 nm from CO chemisorptions, which is in accordance with

X. Song et al. / Catalysis Communications 19 (2012) 100–104
103
Fig. 3. TEM and HRTEM images of (a) OMC, (b) FeOMC, (c) MnOMC, (d) MnFeOMC,(e)Fe particles embedded in FeOMC,(f) Fe0.099Mn0.901O particles embedded in MnFeOMC.
the spatial limitation of the nano-channel (Table 2). The synergistic
effect of the difficult reduction of embedded metal oxide nanoparti-
cles, their intamite interaction with Rh particles, nano-channel, and
graphitic structure might be the reasons for the high activity and
ethanol selectivity of Rh based catalyst supported on the bimetal
modified OMC.
Table 2
CO hydrogenation data on different catalysts.
Catalystsa
Particle size
d (nm)b
T
(K)
P
GHSV
CO
Con%
Selectivity (%)
C2+oxyc
Ref.
−1
(MPa)
(h
)
EtOH
CH
4
CHd
CO
2
MeOH
RhMnFe/OMC
RhFe/MnOMC
RhMn/FeOMC
Rh/MnFeOMC
2.4
2.6
2.8
2.5
573
573
573
573
593
5.0
5.0
5.0
5.0
3.0
12,000
12,000
12,000
12,000
12,000
3.2
16.2
15.5
25.5
8.9
38.0
44.6
41.9
46.3
40.2
24.0
28.7
28.8
34.5
22.7
41.8
29.4
27.7
30.7
47.6
34.9
34.7
38.5
58.2
4.5
9.9
8.6
7.0
3.7
1.6
This work
This work
This work
This work
[20]
11.9
16.4
11.5
e
e
e
RhMnFe/SiO
2
–
–
–
a
Fe loading on RhFe/MnOMC, Mn loading on RhMn/FeOMC and Mn, Fe loadings on OMC have been optimized (see Fig. S1).
Assuming CO/Rhsurface =1.
C2+oxy denotes oxygenates containing two and more carbon atoms such as ethanol, acetaldehyde, and acetic acid.
CH denotes all the hydrocarbons.
b
c
d
e
The data in the indexed paper was not given.

104
X. Song et al. / Catalysis Communications 19 (2012) 100–104
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4
In summary, we have developed a one-pot route for imbedding
[
[
[
[
highly dispersed nanoparticles of iron, manganese, and bimetal iron
manganese oxide into the carbon framework of OMC materials.
These materials were used as the carriers of Rh catalysts for ethanol
synthesis from CO hydrogenation reaction and exhibited excellent
performance, particularly, over the Rh catalyst supported on the bimetal
modified OMC material.
[
[
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[
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