Wheat flour-derived N-doped mesoporous carbon extrudate as superior metal-free catalysts for acetylene hydrochlorination

Article abstract of DOI:10.1039/c7cc09370e

N-Doped mesoporous carbon extrudate with a major quaternary N species has been successfully prepared through direct carbonization of wheat flour/gluten with silica, which is a cheap and convenient method for scale-up production approach. The obtained carbon extrudate metal-free catalyst enables highly efficient production of vinyl chloride monomer through acetylene hydrochlorination, with a superior catalytic performance and excellent stability (>85% conversion and vinyl chloride selectivity over 99% at 220 °C).

Full text of DOI:10.1039/c7cc09370e

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
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Wheat flour derived N-doped mesoporous carbons extrudate as
superior metal-free catalysts for acetylene hydrochlorination
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
b
a
a
Guojun Lan , Yan Wang , Yiyang Qiu , Xiaolong Wang , Ji Liang , Wenfeng Han , Haodong Tang ,
a
c,d
a
Huazhang Liu , Jian Liu* and Ying Li*
DOI: 10.1039/x0xx00000x
www.rsc.org/
N-doped mesoporous carbons extrudate with major quaternary N have been explored as novel catalysts for acetylene
[
4b, 4c, 5, 6]
species are successfully prepared through a direct carbonization of hydrochlorination.
wheat flour/gluten with silica, which is a cheap and convenient for nanotubes (N-CNTs) can enhance the formation of the
scale-up production approach. The obtained carbon extrudate covalent bond between C and N-CNTs to promote the
For example, N-doped carbon
2 2
H
[5]
metal-free catalyst enables the high efficient production of VCM catalytic activity for acetylene hydrochlorination. Bao and co-
through acetylene hydrochlorination, with a superior catalytic workers demonstrated that a nanocomposite of N-doped
performance and excellent stability (>85% conversion and vinyl carbon derived from silicon carbide has an excellent
o
chloride selectivity over 99% at 220 C).
performance for acetylene hydrochlorination with
a
-1 [4c]
conversion of 80% at 200 °C, 30 h . Although it has been
demonstrated that the N-doped carbon materials are active
and promising metal-free catalysts for acetylene
hydrochlorination, it still remains challenging to develop and
scale up the fabrication of N-doped carbon materials through
The vinyl chloride monomer (VCM) has been widely used to
manufacture polyvinyl chloride (PVC), which is the raw
chemical for a wide range of engineering plastics. The
production of VCM is mainly through the acetylene
hydrochlorination reaction, utilizing activated carbon
[7]
facile, green, and low-cost routes.
supported mercury (II) chloride (HgCl /AC) as the catalyst,
2
In the past decade, the utilization of biomass to obtain
carbonaceous materials has attracted much research and
which is highly toxic and harmful to both human health and
[1]
[8]
environment.
The pioneering work and systematic studies
industrial interest. Different biomass such as glucose,
sucrose, fructose, starch, furfural, dopamine, and grass have
been tried as renewable and cheap precursors for
nanocarbons. Among them, the carbon materials prepared via
starch (i.e. Starbon®) have gained much attention due to their
high surface area, tuneable surface chemistry, and controllable
electrical conductivity. In addition, starch is a sustainable,
reusable, and environmentally benign material, that is easy to
carried out by Hutchings and co-workers showed that AuCl3
might be the best replacement of HgCl2 for this process
because of its high activity. Johnson Matthey technology
claimed the successful commercialization gold catalysts with
[2]
low loading and thiosulfate as ligand in 2016 . Despite the
recent commercialization of gold catalysts for acetylene
hydrochlorination, it is still a demand to exploration of new
low-cost catalysts system with high activity and stability.
Doping of carbons by nitrogen modifies not only the
carbon surface chemistry but also the electronic structure by
donating a lone pair of electrons on the undoped carbon
lattice, which may enhance the adsorption of HCl and activate
[9]
form composites in particulate/monolithic forms. However,
the Starbon® prepared from pure starch does not contain N
dopant, and the active sites have to be introduced by
[10]
additional nitrogen precursors, either in-situly or ex-situly.
Compared with starch, natural wheat flour contains abundant
gluten (ca. 10-12%) and certain amount of fat, vitamins,
[4]
acetylene. To this end, various N-doped carbon materials
[
11]
minerals, etc (ca. 13-20%), which are all rich in nitrogen.
Every year, about 700 million tons of wheat is produced
worldwide, and gluten is one of the main by-products in the
[12]
wheat industry, which needs to be removed in some cases
because of the gluten-related health issues. These factors thus
make it very convenient to directly utilize wheat flour and/or
gluten as naturally abundant and low-cost precursors for N-
doped carbons to catalyze the acetylene hydrochlorination.
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Based on these considerations and inspired by the flour- for N-MC-W and 4.2% for N-MC-G, respectively. The higher N
based food cooking method, herein, we for the first time content in the N-MC-G can be attributed to the higher N
demonstrate
a facile and easily scaled-up method to content in gluten than in flour. In contrast, the materials
synthesize N-doped mesoporous carbon, using wheat flour or derived from sucrose (MC-Su) or starch (MC-St) contain much
gluten as both C and N precursors without any other additional lower N contents (0.5 and 0.3%, respectively), possibly due to
nitrogen source. Scheme 1 describes the preparation process experimental error or comes from the impurities of the raw
for N-doped mesoporous carbon (N-MCs) from wheat flour materials. The distribution of the elements was subsequently
and silica spheres (i.e. the hard template for mesopores). The traced by elemental mapping under energy-filtered TEM
mixture of these components was made into dough by adding (Figure 1d-f and S4), which shows a homogeneous distribution
a suitable amount of deionized water. This dough can be easily of both C, N, and O in the materials and indicates the large
and controllably made into any desirable shapes. In this study, amount of N active sites throughout the materials.
it was made into cylinder-shaped extrudate (ф2.5×30 mm)
using a home-made noodle machine (Figure S1-2). These
o
extrudate were then subjected to carbonization at 850 C in an
inert atmosphere and subsequent HF etching to remove the
silica templates. After these treatments, the cylinder shape of
the material can be well-maintained, which is hard to achieve
in other methods and is extremely important for acetylene
hydrochlorination in the fix-bed reactors. For comparison, pure
starch (derived from corn flour) and gluten, are used as
precursors to prepare the mesoporous carbons, which are
denoted as MC-St, N-MC-G, respectively. MC-Su sample was
prepared by using sucrose as carbon source and a MCN sample
was prepared by using ethylenediamine and carbon
tetrachloride as carbon and nitrogen precursors according to
2
Figure 1. N sorption and pore size distribution (a), HRTEM (b) and STEM (c) and C (d),
N (e), and O (f) element mapping for N-MC-W.
[13-14]
references
for comparison.
Table 1 texture properties and elemental composition of various carbons.
Deac
Tivati
on
Elements Composition (%)
S. A.
P. V.
a
2
3
P.D
Samples
( m
( cm
−1
−1
(nm)
C
H
N
O
g
)
g
)
(%
−1 b
h
)
AC
1038
862
715
672
582
0.52
1.25
0.60
0.86
0.75
1.8
9.7
9.7
9.7
9.7
0.40
0.61
0.22
0.16
0.04
91.1
87.1
85.8
80.9
81.2
0.8 <0.3
2.6 <0.3
1.4 <0.3
7.8
9.5
MC-Su
MC-St
12.5
15.8
12.6
Scheme 1. The preparation process of the nitrogen doped mesoporous carbon N-MC-
N-MC-W
N-MC-G
N-MC-G-
used
1.7
1.8
1.6
4.2
W using wheat flour as C&N sources.
4
50
0.69
0.55
9.6
4.5
-
84.3
70.6
1.5
4.7
9.5
The porosity of the materials was investigated by nitrogen
adsorption-desorption technique (Figure 1a, Figure S3).
Typically, the materials possess type IV isotherms with an H1
MCN
422
1.20
2.3 16.5
10.8
[a]calculated based on BJH method; [b] calculated based on the conversion of
hysteresis loop extending from middle to high pressure region, acetylene (X10h-X30h)/20h.
indicating the existence of both mesopores and macropores on
2
the material. The specific surface area of N-MC-W is 672 m g
−1
The catalytic activity of these N-doped mesoporous
3
−1
carbons was evaluated for acetylene hydrochlorination at 220
o
and the pore volume is 0.86 cm g , which are on the similar
level as the other analogues (Table 1). The pore size
distribution of the materials is then calculated by the Barrett-
Joyner-Halenda method, which is centred at ca. 9.7 nm in the
mesopore region for all the materials (inset of Figure 1a). The
micro-structure of the materials was then studied by
transmission electron microscopy (TEM, Figure 1b, c). Large
amount of mesopores can be clearly observed on the material,
which is consistent with the results of the nitrogen adsorption-
desorption results.
-1
C and space velocity of 30 h (Figure 2a). Both N-MC-W from
wheat flour and N-MC-G from gluten show a high acetylene
conversion of 73.3% and 85.5%, respectively. In comparison,
MC-Su and MC-St, prepared from sucrose and starch as carbon
2 2
precursors, have a C H conversion lower than 30%. The
relatively higher performance of N-MC-G than N-MC-W can be
the results of its higher N content. Figure S5 gives the TPD-MS
profiles corresponding to the MC-Su, MC-St, N-MC-W and N-
2
MC-G. It can be seen that the amounts of CO and CO
desorbed for these catalysts are similar, which are in
accordance with the element analysis. These results indicate
The chemical composition of the materials was then
studied by element analysis (Table 1). The N contents are 1.6%
2
| J. Name., 2012, 00, 1-3
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that the oxygen-containing group is not the main reason for the roles of the nitrogen species during the catalysis and to
the big difference of activity. Consequently, N-MC-G and N- identify the deactivation mechanism of the materials, we then
MC-W are readily suitable for acetylene hydrochlorination; conducted X-ray photo electron spectroscopy on the fresh and
while MC-Su and MC-St are less favorable unless further used catalysts (Figure 2b and d). The XPS spectra of N-MC-W
treatments.
and N-MC-G can be deconvoluted into four peaks, which are
assigned to pyridinic (398.3 ± 0.2 eV), pyrrolic (400.0 ± 0.2 eV),
quaternary (401.1 ± 0.2 eV) and oxidized (403.0-405.6 eV) N
a 8
b
N-MC-W
Quaternary N
[
11a, 16]
0
N-MC-G
N-MC-W
Pyrrolic N
species, respectively.
The fitting analysis data shows that
60
40
20
0
Pyridinic
N
the main N specie in N-MC-W and N-MC-G are the quaternary
nitrogen, which is around 60% in the samples (Figure S7a).
While the major N species in MCN are pyrolic N and pyridinic
N, which contributed above 75% to all N species.
Oxidized N
MC-Su
MC-St
5
10
15
20
25
30
406 404 402 400 398 396 394
Binding Energy (eV)
Time on stream (h)
c
90
N-MC-G
d
In present work, on the apparent, the activity of N-MC-G
with quaternary nitrogen as main N specie is more active than
MCN with pyrolic N and pyridinic N as main N specie. However
the current catalytic activity comparison in N-doped carbon
materials is based on the N species contents. Bao et al.
indicate that acetylene hardly adsorbs on the quaternary and
pyridinic N sites because of the endothermic nature of the
adsorption process and they concluded that carbon atoms
N-MC-G
75
Pyridinic
Pyrrolic N
Quaternary N
Oxidized N
N
60
MCN
AC
45
30
15
MCN
0
0
20
40
60
80
100
406 404 402 400 398 396 394
Binding Energy (eV)
Time on stream (h)
Figure 2 (a): The performance of various mesoporous carbon N-MC-G, N-MC-W, MC-Su
o
and MC-St in acetylene hydrochlorination. Reaction conditions: 220 C, 0.1 MPa, GHSV
-
1
=
30 h ; (b): N1s XPS spectra of N-MC-W; (c): The stability test of N-MC-G, AC, and MCN
[4c]
o
-1
bonded with pyrrolic N atoms are the active sites. Kang et al.
summarized that the defects in graphene could efficiently
in acetylene hydrochlorination. Reaction conditions: 220 C, 0.1 MPa, GHSV = 30 h ; (d):
N1s XPS spectra of N-MC-G and MCN.
[
17]
improve the catalytic performance to DFT calculated results.
Therefore the origin of catalytic activity in carbon materials is
affiliated to the status of carbon atom. The surface oxygen
functional groups, edge dangling bonds, and defective sites in
nanocarbon materials may also contribute to their catalytic
activity. The contribution of different N species in active sites
in different carbon materials may different. As reported in
references, Wei et al. reported that the quaternary N is the
biggest contributing N-containing form in N-doped carbon
The stability of the carbon materials in gas phase reaction
is critical. The N-MC-G was then tested for acetylene
o
-1
hydrochlorination at 220 C, 30 h for 100 hours, in
comparison with the commercial activated carbon and MCN
(Figure 2b), and the corresponding deactivation rates of
various carbon materials are summarized in Table 1. It is
noticeable that, apart from their much higher catalytic activity,
the N-MC-G and N-MC-W also have significantly lower
deactivation rates (0.04 and 0.16%/h) compared with other
materials (in the range of 0.22-1.20%/h). It is remarkable that,
among the materials, the N-MC-G possesses the lowest
deactivation rate, which is almost one-fold lower than that of
AC (the detailed characterization of activated carbon was given
[5]
nanotubes. While Dai et al. demonstrated that pyrrolic N is
the most important nitrogen species graphitic carbon nitride
[4b]
and N-doped active carbon catalyst. Li et al. indicated the
pyridinic N are the active sites in N-doped porous carbon
[6a]
derived from ZIF-8.
[
15]
After the long-term stability test, the sample (denoted as
N-MC-G-used) was subsequently analysed to further identify
the stability of various N species during the catalysis. From the
elemental analysis data given in Table 1, it can be found that
the N content for the fresh and used catalysts are 4.2 and
in our previous work
). It should be notes that although
MCN samples has very high N loadings (15.4 wt%), its
conversion of acetylene and stability is lower than that of N-
MC-G and N-MC-W samples. The MCN have lower surface area
and a smaller pore size compared with N-MC-G. But these
differences will not make the big difference in catalytic
performance. From Table 1, it can be seen that the surface
area of N-MC-G and N-MC-W are lower than MC-St and MC-
Su. But the activity is much higher. This result indicates that
the surface area has smaller effect than that of N contents.
The graphitization degree of N-MC-G and MCN are
characterized by XRD and Raman spectroscopy, given in Figure
S6. It can be seen that XRD pattern and Raman spectra of the
4
.7%, respectively. The C content increases from and 81.2 to
4.3% and the oxygen content decreases from 12.6% to 9.5%.
8
In comparison, the XPS survey scan shows that the surface N
contents of N-MC-G subjected to a larger amount of decrease
after the 100 h reaction (5.7% vs. 4.5%, Table S1). The actual
content of quaternary N for the spent N-MC-G catalyst is
decreased compared with the fresh N-MC-G catalyst. (For the
fresh N-MC-G catalyst, the loading of quaternary N=
5.67%×59.97% = 3.40%; for the spent N-MC-G catalyst the
D G
N-MC-G and MCN and calculated I /I ratios are similar. These
loading of quaternary N= 4.48% × 62.89% = 2.85%).
Considering the low detection depth of XPS technique, the
inconsistent results of elemental analysis and XPS results
consequently reveal that it is mainly the surface N species that
significantly decreased during the test, while the bulk N
species remains. This may be caused by the carbon deposition
on the surface of the catalyst and which is further been
results indicate that the graphitic degree is not the main
reason for the big difference of activity.
Great efforts has been made from various research groups
to identify the active sites of N doped carbon materials in
acetylene hydrochlorination by using experimental and theory
calculations methods, however, the role of different N species
[
1,3-5]
in active sites is still under debate
.To better understand
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approved by the loss of the surface area (Table 1). By Science Foundation of Zhejiang Province (LY17B030010) is
comparing the nitrogen adsorption-desorption isotherms and gratefully acknowledged
pore size distributions of the fresh and used N-MC-G (Figure
S8), it can be seen that the isotherm curves are similar,
Notes and references
indicates that the carbon deposition is not heavy. But most of
micropore and parts of mesopore are blocked from pore size
distributions. This may seriously affect the mass transfer of
reactants. The mass loss of fresh and used N-MC-G catalysts
under an oxygen atmosphere is compared in Figure S9. The
coke deposition is only 0.66% calculated based on the mass
loss differences of N-MC-G and N-MC-G-used in the 100-450
oC range. That means the coke deposition occurs but not very
heavy, this is consistent with the low deactivation rate of this
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7
28.
In conclusion, the N-doped mesoporous carbons were
successfully prepared by using wheat flour or gluten as both
carbon and nitrogen source, which shows high activity and
stability for acetylene hydrochlorination as a metal free
catalyst. The wheat flour, an excellent natural-born mixture of
starch with gluten, is an excellent C and N precursor to prepare
N-MCs with homogenously distributed N atom doped as
graphitic framework active site, and the sticky properties of
gluten make the shape of the final carbon materials easier and
more convenience. The wheat flour derived granular N-doped
mesoporous carbon have many remarkable advantages which
make them ideal catalysts for a number of key industrial
processes: (i) highly homogeneous distribution of the
heteroatom dopants (N) within the composite; (ii) easy, cost-
effective, and environmentally safe raw material for upscale
syntheses. (iii) 3D shaped open-cell structures with low mass
transfer limitation and relatively high surface area. The
kilogram scale preparation of the gluten derived N dope
mesoporous carbon is under investigations in our lab.
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There are no conflicts to declare.
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The authors would like to thank for Professor Xianping Yao in
Hangzhou research institute of chemical technology Co Ltd for
providing the starch sample and fruitful disscusion for
understanding the properties of the starch and related
materials. The financial support from Natural Science
Foundation of China (NSFC Grant No. 21776257) and Natural
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DOI: 10.1039/C7CC09370E
Table of Contents
Granular N-doped mesoporous carbons extrudate are successfully prepared through a food
cooking inspired easy shaped method by using wheat flour/gluten as both carbon and nitrogen
sources. This biomass derived metal-free N-doped mesoporous carbons featured superior catalytic
performance and excellent stability for acetylene hydrochlorination.