N-doped graphene as an electron donor of iron catalysts for CO hydrogenation to light olefins

Article abstract of DOI:10.1039/c4cc06600f

N-doped graphene used as an efficient electron donor of iron catalysts for CO hydrogenation can achieve a high selectivity of around 50% for light olefins, significantly superior to the selectivity of iron catalysts on conventional carbon materials, e.g. carbon black with a selectivity of around 30% at the same reaction conditions. This journal is

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Communication
N-doped Graphene as an Electron Donor of Iron Catalyst for CO
Hydrogenation to Light Olefins
a
*a
a
b
*a
Xiaoqi Chen , Dehui Deng , Xiulian Pan , Yongfeng Hu , and Xinhe Bao
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
N-doped graphene used as an efficient electron donor of iron 45 support due to its high surface area and exotic electronic
2
5ꢀ27
catalyst for CO hydrogenation can achieve a high selectivity
of around 50% for light olefins, significantly superior to the
selectivity of iron catalyst on conventional carbon materials,
e.g. carbon black with a selectivity of around 30% at the same
reaction conditions.
properties.
However, perfect graphene is inert in chemistry. It
is reported that doping heteroatoms such N and B atoms into the
matrix of graphene can tailor its electronic structure and chemical
activity, which can be used as an electron donor or acceptor
1
0
28ꢀ32
50
according to the types of dopants.
Inspired by this, we report
herein that the Nꢀdoped graphene can be used as an efficient
electron donor for iron catalyst to enhance the performance of CO
hydrogenation to light olefins.
CO hydrogenation to light olefins is regarded as one of the most
important conversion ways of methane (natural gas and shale gas)
1
ꢀ4
and coal to chemical feedstock and fuels. Especially, with the
increasing discovery of shale gas, several governments such as
America, Canada and China, have given more attentions to
methane conversion. Therefore, CO hydrogenation to light
olefins has become a hot topic in the field of energy and chemical
engineering. However, due to the limit of AndersonꢀSchulzꢀFlory
(ASF) distribution in FischerꢀTropsch (FT) synthesis, most
products of CO hydrogenation are saturated alkanes and long
5
5
Nꢀdoped graphene (NG) was synthesized by an oneꢀpot
solvothermal method with the Li N and CCl as the precursors as
our previous report. The nitrogen content in NG can be
efficiently controlled with the aid of the cyanuric chloride during
the reaction (see supporting information for more details). In this
study, three different nitrogen content, i.e. 4.5%, 8.4%, 16.4%
1
2
2
3
3
4
5
0
5
0
5
0
3
4
33
60
(N/C) in NG was prepared according to the Xꢀray photoelectron
5
,
6
spectroscopy (XPS) measurement (Figure S1,2 and Table S1),
which was denoted as NGꢀ4.5, NGꢀ8.4 and NGꢀ16.4, respectively.
The Raman spectra (Figure S5) showed that these NG samples
chain hydrocarbons.
distribution for light olefins with high selectivity.
metals including Fe, Co, Ni and Ru are often used as the catalysts
It is difficult to control the product
7
ꢀ10
Different
ꢀ
1
ꢀ1
1, 11
65 had the characteristic D (1335 cm ), G (1585 cm ) and 2D (2660
for CO hydrogenation.
Among them, Fe based nanomaterials
ꢀ
1
cm ) bands of graphene, and the G bands split into two peaks
have been regarded as the lowꢀcost, highꢀefficient catalysts to
enhance the selectivity of light olefins in CO hydrogenation.
Previous research indicated that the iron based catalysts for light
olefins are very sensitive to the electronic properties of the
additives and supports. For example, Na and K additives can be
used as the electron donor to increase the selectivity of the light
ꢀ
1
with a D’ band at 1620 cm probably introduced by nitrogen
doping which was also observed in nitrogenꢀdoped graphene by
3
4, 35
other preparation methods.
samples (Fe/NG) via an ultrasoundꢀassisted impregnation method
see supporting information for more details), which was denoted
as Fe/NGꢀ4.5 Fe/NGꢀ8.4 and Fe/NGꢀ16.4 respectively. For
comparison, we also prepared XCꢀ72 and nitrogen doped XCꢀ72
denoted as XCꢀN) loading iron catalysts, which was denoted as
The iron was loaded on NG
70
(
1
2ꢀ14
,
,
olefins.
Different supports such as silica, alumina, magnesia,
zeolite, carbon, SiC etc. also have a crucial effect on the
selectivity of these catalysts due to the different electronic
(
1
3, 15ꢀ21
75 Fe/XC and Fe/XCꢀN, respectively (see supporting information for
more details). The iron content in all samples is around 8 wt.%
according to the inductively coupled plasma optical emission
spectrometry (ICPꢀOES) analysis in Table S2.
interactions between them.
Among them, carbon materials
have attracted great attentions as the potential candidate because
of their unique structural and electronic properties. For example,
our previous research showed that Fe catalysts confined inside
carbon nanotubes (CNTs) can significantly affect the catalytic
selectivity of CO hydrogenation compared with the Fe catalysts
supported on the outside of CNTs due to the different electronic
80
TEM images showed the morphology and structure of these
Fe/NG samples. Taking any scanning area of the samples, one
can see the morphology of Fe/NG samples (Figure 1b and S9)
remain nanosheet structure as the original NG samples (Figure
2
2ꢀ24
environment inside and outside the CNTs.
1
a). HRTEM images showed that these nanosheets in Fe/NG
Recently, graphene has attracted wide attention as a catalyst
85
contain wellꢀdispersed nanoparticles with an average size of c.a.
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4
nm. The planar d of these particles is 2.57±0.05 Å,
a) 100
Fe/NG-4.5
b)100
FeNG-8.4
corresponding to [110] plane of hematite (Fe O ), in accord with
2
3
CH
4
CH
4
the XRD analysis (Figure S6).
80
80
60
40
20
0
=
2
=
4
=
2
=
4
C
-C
C -C
6
4
2
0
0
0
0
C
2
-C
4
C
2
-C
4
C
5+
C5+
o
C
o
C
o
C
o
C
o
C
o
C
o
C
o
C
320
340
360
340
320
340
360
340
0.5 MPa
0.5 MPa
0.5 MPa
1.0 MPa
0.5 MPa
0.5 MPa
0.5 MPa
1.0 MPa
7
0
c) 1
00
Fe/NG-16.4 d)
Fe/XC
Fe/XC-N
60
CH4
Fe/NG-16.4
80
50
6
0
C2
=
-C4
=
40
30
20
40
2
0
2
C -C4
10
0
C
5+
0
o
C
o
o
C
o
o
o
C
o
C
o
320
C
340
360
C
340
C
320
340
360
340
C
0.5 MPa
0.5 MPa
0.5 MPa
1.0 MPa
0.5 MPa
0.5 MPa
0.5 MPa
1.0 MPa
40
Figure 2. The performance of CO hydrogenation to light olefins
by Fe/NG catalysts. The product distribution of CO
hydrogenation by Fe/NGꢀ4.5 (a), Fe/NGꢀ8.4 (b) and Fe/NG
at various reaction temperature and pressure. (d) C ꢀC
(c)
ꢀ16.4
=
2
=
4
selectivity of Fe/XC, Fe/XCꢀN and Fe/NGꢀ16.4 at various
5
Figure 1. The morphology and structure of NG and Fe/NG
samples. (a) TEM image of NGꢀ16.4. (b) TEM image and (c)
HRTEM image of Fe/NGꢀ16.4 before reaction. The area with red
dashed circles in (c) shows the dispersed Fe O nanoparticles on
4
5
reaction temperature and pressure. Reaction condition: 100 mg
ꢀ1
catalyst, Fe loading = 8 wt.%, GHSV = 5000 h , H : CO = 1:1.
2
2
3
To further confirm the nitrogen doping effect to CO
hydrogenation, we also test the catalytic reaction by using iron
the graphene nanosheets. The insert in (c) shows the size
1
0
distribution of Fe O nanoparticles. The Fe/NG samples were
2
o
3
50 catalyst supported on pure conductive carbon black (XCꢀ72) and
nitrogen doped XCꢀ72 (XCꢀN). As shown in Table S4, the light
olefins selectivity of Fe/XC is only 29.0% and 17.5% in 0.5 MPa
first treated at 350 C in Ar for 1 h before TEM measurement.
o
and 1 MPa at 340 C, respectively. In comparison, the light
CO hydrogenation was carried out on a fix bed reactor using a
olefins selectivity of Fe/XCꢀN significantly increase to 35.6%
55 and 35.9% in 0.5 MPa and 1.0 MPa, respectively. Nevertheless,
the selectivity of light olefins of Fe/XCꢀN is still lower than that
of Fe/NG samples at the same conditions (Figure 2d), which may
be attributed to the NG samples possess more nitrogen content
than XCꢀN sample, as shown in Table S1. This result further
typical syngas with a H /CO radio of 1:1. The reaction was first
2
o
1
2
2
3
3
5
0
5
0
5
performed at 340 C with a pressure of 0.5 MPa and a gas hourly
ꢀ
1
space velocity (GHSV) of 5000 h . After reaching the preꢀset
temperature, the reaction was continued at least 8 hours to get a
steady state. It should be noted that the there was no obvious
activity for pure NG samples since the CO conversion was almost
negligible (lower than 0.1%). The activity and selectivity of
Fe/NG samples were summarized in Table S3 and Figure 2. One
can see that all Fe/NG catalysts showed high selectivity, i.e.
around 50% towards light olefins in all CH products at 0.5 MPa.
When increasing the pressure to 1.0 MPa, the CO conversion will
significantly increase while the selectivity of light olefins will
reduce but still more than 40%. It is quite remarkable since iron
based catalysts usually give a wide distribution of hydrocarbons
with a low selectivity toward light olefins (usually no more than
60
convinced that the introduction of nitrogen atom in graphene can
enhance the selectivity of CO hydrogenation to light olefins.
Table 1. The performance of CO hydrogenation by Fe/NGꢀ16.4
catalyst at various space velocity.
ꢀ
1
GHSV (h )
CO conversion (%) 1.4
CO selectivity (%) 11.5
CH distribution (%)
5000
2000
3.2
1000
8.8
600
21.1
35.1
2
14.2
22.6
CH
4
37.8
48.2
8.2
35.8
47.0
5.6
28.7
48.0
4.5
21.4
49.6
5.4
4
0%) when directly supported on carbon materials without
=
=
1
0, 12, 14
C
2
ꢀC
=
4
promoters like S, K and Mn.
The nitrogen here may play
=
4
0
0
4
(C
2
ꢀC
)/(C
2
ꢀC
)
the role like the K and Mn promoters that inhibited the
hydrogenation of olefins and thus increased the selectivity of
olefins. In addition, as shown in Table S3, with nitrogen content
increasing from 4.5% to 16.4%, CH4 selectivity will increase
from 14.2% to 29.2%, while the selectivity of C will reduce
C
5+
8.1
8.8
12.7
19.8
65
Reaction condition: 100 mg catalyst, Fe loading = 8 wt.%, H :
2
o
CO = 1:1, 340 C, P = 0.5 MPa.
5
+
ꢀ
1
o
Apart from the selectivity enhancing with the nitrogen content
increasing, we also found that increasing N content in Fe/NG
samples can promote the CO conversion, i.e. with the N content
increasing from 4.5% to 16.4%, the CO conversion increases
from 39.4% to 15.5% at GHSV = 5000 h , 340 C and 1.0 MPa,
indicating that the growth of carbon chain was also restrained by
increasing the nitrogen content.
70
o
from 1.3% to 5.0% at 340 C under 1 MPa. We speculate that the
introduction of nitrogen may introduce more defects in graphene
2
|
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1, 42
and subsequently promote the dispersion of the iron particles as 45 according to the literature.
Therefore, the decrease of Lꢀedge
3
6, 37
shown in XRD spectra (Figure S6).
The nitrogen promotion
peak intensity of the iron means iron gets more electrons at the 3d
final state, suggesting that the introduction of N promotes the
electron transfer from NG to iron. Furthermore, XANES Fe Kꢀ
edge shows the Fe/NG samples after reaction possess more
to the dispersion of metal particles in carbon materials was also
demonstrated in the literature. For examples, Hu and his coꢀ
workers have demonstrated that Pt loaded on Nꢀdoped carbon
5
nanotubes shows higher electrocatalytic activity than that on pure 50 reduced state of iron compared with Fe/XC sample (Figure 4c).
carbon nanotubes, which was attributed to better dispersion of Pt
Further Fourierꢀtransformed extended Xꢀray adsorption fine
structure also indicates that the Fe/NG samples has a FeꢀC bond
at 1.4 Å and a FeꢀFe bond at 2.1 Å while the Fe/XC sample
shows a double peak feature, i.e. a broad FeꢀO bond at 1.4 Å
3
8
nanoparticles on Nꢀdoped carbon nanotubes. In addition, we
also studied the catalytic performance of the Fe/NG samples with
the effect of GHSV. As shown in Table 1, with decreasing GHSV
1
1
2
2
0
5
0
5
ꢀ
1
ꢀ1
of Fe/NGꢀ16.4 from 5000 h to 600 h , the CO conversion 55 (overlapped with FeꢀC bond) and a FeꢀOꢀFe bond stretched to 2.6
o
increases significantly, i.e. from 1.4% to 21.1% at 340 C and 0.5
MPa, while the selectivity of light olefins still remains around
Å, corresponding to the feature of Fe O . XRD patterns further
2 3
confirmed that the iron mainly remains lowꢀvalence state in
Fe/NG samples after reaction. As shown in Figure 4b, there are
two main phases, i.e. the peaks at 42.6° and 44.9° corresponding
5
0%. It is reported that the carbon chain growth increased with
=
=
the decreasing GHSV, and usually lead a lower C ꢀC
selectivity according to the literature. So it is surprising to find 60 to the [102] and [211] phase of Fe C , respectively, and the peaks
that the Fe/NG catalysts can still keep high C ꢀC selectivity at
2
4
8
7
3
=
=
at 43.4° and 44.0° corresponding to the [021] and [510] phases of
Hägg Fe C , respectively, which is known as an active phase in
2
4
a lower GHSV since this high selectivity is often only gained by
adding promoters like K and Mn or at a very high GHSV (usually
5
2
6, 43, 44
Fischer ꢀ Tropsch synthesis.
These broad and weak peaks in
ꢀ
1 13, 39
over 10000 h ).
Furthermore, the optimized Fe/NGꢀ16.4 also
Fe/NGꢀFT samples also imply that these iron carbide species
65 formed after reaction are still highly dispersed. These results
indicate that graphene doped with N can offer the electron to keep
iron particles at a low chemical valence state, which is similar
with the role of alkali metal promoters in conventional FT
synthesis and therefore enhance the selectivity of light olefins for
=
=
shows longꢀterm stability toward CO conversion and C ꢀC
2
4
selectivity during the lifetime test of 90 h (Figure 3). These
results indicate that the introduction of nitrogen in Fe/NG
samples can significantly enhance both the activity and selectivity
for CO hydrogenation to light olefins with a high durability.
70
CO hydrogenation.
5
5
4
5
0
5
a)
Fe/XC
Fe/NG-4.5
b)
◆
▽
▲
Fe
Fe
C
C
5
2
▲
L
3
edge
7
C
3
Fe/NG-8.4
Fe/NG-16.4
◆◆
▽
▽
▽
▽
◆
◆
Fe/NG-4.5-FT
Fe/NG-8.4-FT
L
2
edge
Fe/NG-16.4-FT
Fe/XC-FT
1
0
5
0
700
710
Energy (eV)
720
730
20
30
40
50
60
70
2
- Theta (dgree)
c)
Fe
O
d)
Fe-Fe
2
3
Fe/XC-FT
Fe/NG-16.4-FT
Fe-C (Fe-O)
Fe-O-Fe
Fe/NG-4.5-FT
Fe/NG-8.4-FT
Fe/NG-16.4-FT
Fe/XC-FT
Fe/NG-8.4-FT
Fe/NG-4.5-FT
Fe foil
0
20
40
60
80
Time on stream (h)
Fe foil
Fe O
2
3
Figure 3. Life test of CO hydrogenation by Fe/NGꢀ16.4 catalyst.
Reaction condition: 100 mg catalyst, Fe loading = 8 wt.%, GHSV
7100
7120
7140
7160
7180
7200
0
2
4
6
Energy (eV)
R (Å)
ꢀ
1
o
=
2000 h , H : CO = 1 : 1. Temperature = 340 C, P = 0.5 MPa.
Figure 4. Structural and electronic characterization of the Fe/NG
and Fe/XC samples before and after CO hydrogenation. (a)
Normalized XAS of Fe Lꢀedge of original Fe/NG and Fe/XC
2
3
3
4
0
5
0
To comprehend the nature of the nitrogen effect to the active
sites of Fe/NG samples for CO hydrogenation, Xꢀray adsorption 75 samples measured in a total electron yield (TEY) mode. The
o
fine structure spectra (XAFS) and Xꢀray diffraction (XRD)
measurements were employed to investigate the structural and
electronic properties of these catalysts before and after the
reaction. Xꢀray absorption spectra (XAS) of Fe Lꢀedge analysis
samples was treated in Ar at 350 C for 1 h before XAS tests. (b)
XRD patterns of Fe/NG and Fe/XC samples after reaction. (c)
Normalized XANES spectra of Fe Kꢀedge of Fe/NG and Fe/XC
samples after reaction compared with standard Fe foil and Fe O
2
3
(
Figure 4a) indicated that the original Fe/NG and Fe/XC samples 80 samples. (d) Fourierꢀtransformed k ꢀweighted EXAFS signal of
3
have a similar energy at the Fe L ꢀedge, corresponding to a
Fe/NG and Fe/XC samples after reaction compared with standard
3
,2
typical Fe O feature, which is in agreement with the XRD
analysis (Figure S6). But the intensity of the L3,2ꢀedge peak in
Fe/NG samples has a significant decrease compared with that in
Fe/XC sample and further decreases with nitrogen content 85 underwent the same reaction condition, i.e. 340 C, GHSV =
increasing. The metal Lꢀedge intensity is proportional to the
number of halfꢀ or unoccupied metal d orbitals in the final state
Fe foil and Fe O samples. Dashed lines are corresponding to the
FeꢀC (FeꢀO) bond (1.4 Å), FeꢀFe bond (2.1 Å) and FeꢀOꢀFe bond
2
3
2
3
4
0
(2.6 Å), respectively. All the samples after CO hydrogenation
o
ꢀ
1
5000 h , 1.0 MPa and time on stream over 80 h.
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In conclusion, we demonstrated that Nꢀdoped graphene can be
used as an efficient electron donor of iron catalyst to enhance the
performance of CO hydrogenation to light olefins. These Fe/NG
samples exhibited a high selectivity toward light olefins with a
longꢀterm durability over 90 h. XAS results of Fe Lꢀedge and Kꢀ
edge and XRD indicated that the iron supported on Nꢀdoped
graphene possess more reduced state before and after the reaction
than that on XCꢀ72, which could be the key factor to promote the
selectivity of light olefins in Fe/NG samples. This study
introduces a new way to enhance the performance of CO
hydrogenation to light olefins and can further promote the
understanding toward the nature of CO hydrogenation.
6
6
7
7
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9
9
0
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0.
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We gratefully acknowledge the financial support from the
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XAFS measurements, and Mr. Fan Zhang for the assistance on
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a
25
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023,
China. Eꢀmail: dhdeng@dicp.ac.cn; xhbao@dicp.ac.cn; Fax: +86ꢀ411ꢀ
3
3
1.
2.
8
437 9128; Tel: +86ꢀ411ꢀ8468 6637
Canadian Light Source Inc., University of Saskatchewan, 44 Innovation
b
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Nꢀdoped graphene was used as an efficient electron donor of iron catalyst to enhance the selectivity of
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