Multiporous Carbon Encapsulated Ni Nanoparticles Promoting Glycerol Valorisation towards Hydrogenation against Rearrangement?

Article abstract of DOI:10.1002/cjoc.201900437

A dual-templating method was used to synthesize a series of hierarchical carbon supports containing different proportions of spherical macropores (ca. 200 nm in diameter) and mesoporous channels (ca. 4 nm in diameter). These and some other conventional carbon materials were subsequently impregnated with Ni and tested for the conversion of glycerol. The hierarchical catalysts exhibited a significantly higher conversion (96%) and selectivity (77%) to 1,2-propanediol, and the specificity selectivity coefficient (6.1) towards 1,2-propanediol against lactic acid was three times higher than that observed over a conventional Ni/C_micro catalyst (2.1). The enhanced performance of these materials, compared with the Ni nanoparticles supported on conventional carbon supports, was attributed to their high surface areas (> 1110 m²?g^?1) and large pore volumes (ca. 0.4 cm³?g^?1) permitting greater accessibility of substrate and/or intermediates to Ni active sites. Given that the concentration of accessible Ni sites in these materials is higher, a competitive benzilic-acid-rearrangement reaction to produce lactic acid was suppressed, leading to an enhanced hydrogenation selectivity to 1,2-propanediol. This study evidences the potential benefits, which can be established from utilizing hierarchical support materials in the valorization of biomass.

Full text of DOI:10.1002/cjoc.201900437

Chinese Journal
of Chemistry
CJC 中 国 化 学 - An International Journal
Accepted Article
Title: Multiporous Carbon Encapsulated Ni Nanoparticles Promote Glycerol
Valorisation towards Hydrogenation against Rearrangement
Authors: Bin Zhang, Bin Chen, Mark Douthwaite, Lipeng Tang, Yibo Zhang,* Meng
Wang, Ding Ma*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.201900437.
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published online in Early View: http://dx.doi.org/10.1002/cjoc.201900437.
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Multiporous Carbon Encapsulated Ni Nanoparticles Promote Glycerol
Valorisation towards Hydrogenation against Rearrangement
Bin Zhang,#, a, b Bin Chen,#, c Mark Douthwaite, Lipeng Tang, Yibo Zhang,* Meng Wang, Ding Ma*
b
a
,c
a
, a
a
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering and College of Engineering, and BIC-ESAT, Peking
University, Beijing, 100871, China.
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, CF10 3AT, UK
b
c
State Key Laboratory of Rare Earth Resources Utilization and Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun 130022, PR China
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX 小
Summary of main observation and conclusion A dual-templating method was used to synthesize a series of hierarchical carbon supports containing
different proportions of spherical macropores (ca. 200 nm in diameter) and mesoporous channels (ca. 4 nm in diameter). These and some other conventional
carbon materials were subsequently impregnated with Ni and tested for the conversion of glycerol. The hierarchical catalysts exhibited a significantly higher
conversion (96%) and selectivity (77%) to 1,2-propanediol, and the specificity selectivity coefficients (6.1) towards 1,2-propanediol against lactic acid was
three times higher than that observed over a conventional Ni/Cmicro catalyst (2.1). The enhanced performance of these materials, compared with the Ni
2
-1
3
-1
nanoparticles supported on conventional carbon supports, was attributed to their high surface areas (> 1110 m g ) and large pore volumes (ca. 0.4 cm g )
permitting greater accessibility of substrate and/or intermediates to Ni active sites. Given that the concentration of accessible Ni sites in these materials is
higher, a competitive Benzilic-acid-rearrangement reaction to produce lactic acid was suppressed, leading to an enhanced hydrogenation selectivity to 1,2-
propanediol This study evidences the potential benefits which can be established from utilizing hierarchical support materials in the valorization of biomass.
particle growth via Ostwald ripening at pH >8.[17]
It has been reported that under alkaline conditions, the catalytic
selectivity to PDO over supported Ni catalysts is directly related to
Background and Originality Content
Biomass is considered to be a promising alternative to
conventional fossil-based feedstocks for the production of
the rate of hydrogenation of intermediates 2-hydroxyacrolein or
[
1]
commodity chemicals and liquid fuels.
[16]
pyruvaldehyde over the Ni sites.
As such, we deduce that
Glycerol is a biomass-derived platform chemical, produced in
large quantities as a by-product from the transesterification of
increasing the accessibility of Ni metal sites would promote the
hydrogenation process. Based on conclusions drawn from our
st
vegetable and animal fats; a key process for the production of 1
[12-16]
previous studies,
a reaction scheme is proposed, documenting
[
2]
generation bio-fuels.
The current global drive to increase
all the potential reaction pathways which could occur, see Scheme 1.
The tandem reaction of glycerol to PDO involves the
dehydrogenation of glycerol (1) to glyceraldehyde (GA, 2), which
dependencies on renewable feedstocks is projected to substantially
increase the industrial production of glycerol over the coming
[18]
[
3]
years. As such, the catalytic conversion of glycerol into high-value
commodity chemicals, such as 1,2-propanediol (PDO), lactic acid
subsequently undergoes dehydration to produce 2-hydroxyacrolein
[16]
(
HA, 3) or pyruvaldehyde (PA, 4). The sequential hydrogenation
[
4, 5]
[6, 7]
(LA)
and ethylene glycol (EG),
has been extensively studied
[19]
of these intermediates leads to the formation of PDO (5).
evident, that the rate of this final hydrogenation reaction influences
the reaction selectivity to LA and PDO, as this hydrogenation
reaction competes directly with the Benzilic-acid-rearrangement
reaction, resulting in the formation of LA (6).
propose that improving the efficiency of this hydrogenation reaction
would indirectly suppress the rearrangement reaction, ultimately
promoting the reaction selectivity to PDO.
It is
and the developments have been documented in a number of
[
3, 8, 9]
reviews.
Among them, the efficient production of PDO from
glycerol can be achieved via developing highly active hydrogenation
catalysts.
[20]
As such, we
Supported Ni catalysts are widely acknowledged to be
[
10]
promising hydrogenation catalysts, but are somewhat limited by
[
11]
their hydrothermal stability.
We have previously reported that
supported Ni catalysts are effective for the hydrogenolysis of
glycerol. A significant deactivation over subsequent uses was
observed, this is attributable to Ni leaching and particle
The use of porous supports has been demonstrated to be highly
effective for improving the activity and stability of Ni nanoparticles
[21-23]
in the hydrogenolysis of cellulose and xylose.
Mesoporosity
[
12-15]
agglomeration.
It was later determined that the deactivation of
can contribute to the anchoring of Ni nanoparticles due to channel
supported Ni catalysts could be suppressed by adjusting the pH of
the reaction solution through the addition of base (e.g. NaOH).
This elegant strategy to stabilize Ni nanoparticles under
hydrothermal conditions, was determined to reduce Ni leaching and
[24]
confinement effects, which promote the stability of supported Ni
[
16]
catalysts under hydrothermal conditions. It can therefore be
postulated that advances in glycerol hydrogenolysis may arise from
the application of multifunctional and hierarchical support materials.
This article has been accepted for publication and undergone full peer review but has not been through
the copyediting, typesetting, pagination and proofreading process which may lead to differences between
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First author et al.
Numerous porous carbon materials, such as carbon nanotubes
polystyrene spheres (PS) and SBA-15 synthesized in-situ from
tetraethyl orthosilicate (TEOS), were used as the templating agents
of macropores and mesopores, respectively. The initial composite
[
25]
[26]
(
CNT), carbon nanofibers (CNF), high-surface-area graphite
[
27]
[28]
[35]
(HSAG) and graphene oxide (GRO) have been investigated as
both catalysts and supports for the hydrogenolysis of glycerol.
However, to date, work in this area has predominantly focused on
the synthesis and testing of mesoporous materials and as such,
investigation into the potential of using hierarchical materials
containing both macro- and mesopores has been somewhat ignored.
It is known that macroporous frameworks benefit diffusion
was prepared by combining TEOS and PS at a weight ratio of 6
(TEOS/PS) in the presence of P123 surfactants. This composite was
subsequently calcined to remove the spheres and formed macro-
mesoporous SBA-15 composite. This was then coated in glucose,
carbonized and etched to remove the silica template. The final
material, denoted as MMC-X (X denotes the ratio of TEOS/PS,
[
29, 30]
process,
internal metal active sites.
leading to increased accessibility of reactants to
3 2 2
herein X = 6), was impregnated with Ni(NO ) ·6H O, calcined and
[
31-33]
As such, we reasoned that the
reduced to yield the final Ni/MMC-6 catalyst (Figure 1a-b). The
images from the electron microscopy confirmed that the material did
indeed consist of larger Ni nanoparticles (ca. 3-7 nm in diameter) in
the macropores (Figure 1a and Figure S2) and a large proportion of
Ni nanoparticles (ca. 2-4 nm in diameter) in mesoporous channels
(Figure 1b and Figure S2). two additional materials with different
proportions of meso- and macro-pores were also synthesized (Figure
c and e). This was achieved by changing the ratio of TEOS and PS
used in the templating stage of the preparation. For the synthesis of
these additional materials, TEOS/PS ratios of 1 and 18 were used;
denoted as MMC-1 and MMC-18, respectively.
application of a hierarchical carbon support, consisting of both
meso- and macro-pores, could reduce the reactant/product mass
transfer limitations and facilitate greater accessibility to Ni active
sites. This in turn, would increase the rate of the hydrogenation
reaction and ultimately, promote reaction selectivity to PDO. Herein,
we describe in detail a method for the synthesis of hierarchical
carbon materials, which possess both macropores (200 nm) and
well-ordered mesoporous channels (4 nm). These materials were
loaded with Ni nanoparticles and investigated for the selective
hydrogenolysis of glycerol to PDO.
Figure 1. (a, b) TEM images of Ni/MMC-6 catalyst. (c, d, e) SEM images of
MMC materials in the proportion of mesopore to macropore (18, 6, 1).
Scheme 1 Proposed reaction scheme for the hydrogenolysis of glycerol
over Ni supported catalysts under alkaline conditions. 1 - Glycerol, 2 –
glyceraldehyde (GA), 3 - 2-hydroxyacrolein (HA), 4 - pyruvaldehyde (PA),
To further understand how the multipores of the support affected
catalytic performance, a number of other carbon supports were also
investigated. These included a microporous carbon material (Cmicro),
carbon nanotubes (CNT) and an additional macropore-free
mesoporous carbon material (MC). The Cmicro and MC materials
were synthesized using the same templating procedure invoked for
the preparation of the MMC-6 catalyst (the absence of templates).
All of these carbons were subsequently impregnated with Ni,
following the same methodology used for the preparation of the
Ni/MMC-6 catalyst.
5
- 1,2-propanediol (PDO), 6 - lactic acid (LA), 7 - ethanol, 8 - ethylene
glycol (EG), 9 - methanol.
Results and Discussion
Synthesis, characterization and testing of the multiporous
carbon catalysts
The textural properties of these carbon catalysts were
Macro-mesoporous carbon materials (MMCs) were synthesized
by the modification of a dual-templating procedure.[34] In detail,
subsequently investigated by N
2
physisorption, the results of which
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are displayed in Table S1 & Figure S2. The measured total surface
area and pore volume for each of the Ni/MMC-X materials were
found to be substantially higher than those determined for the
Ni/Cmicro and Ni/CNT materials. The surface areas of all the
Ni/MMC-X catalysts were all determined to be greater than 1110
2
-1
m ∙g , whereas that of the Ni/Cmicro and Ni/CNT catalysts were
2
-1
substantially lower (~ 250 m ∙g ). In addition, the pore volume of
3
-1
all the Ni/MMC-X catalysts (~ 0.4 cm ∙g ), was determined to be
approximately four times higher than that observed for the Ni/Cmicro
3
-1
and Ni/CNT catalysts (~ 0.1 cm ∙g ).
The Ni catalysts were subsequently tested for the hydrogenolysis
of glycerol under alkaline conditions (20 wt.% glycerol, 0.5 M
NaOH, 4 MPa H , 210 °C, 6 h). The results of these experiments are
2
displayed in Table 1. The presence of macropores in the Ni/MMC-
X catalysts had a pronounced effect on the conversion of glycerol.
Glycerol conversions up to 95 % were observed in the reactions
conducted over the Ni/MMC-X catalysts, which was notably higher
than that exhibited in the reaction over the macropore-free Ni/MC
catalyst (80 %). Lower glycerol conversions were also exhibited by
the Ni/Cmicro and Ni/CNT catalysts. The lowest and highest reaction
selectivity to PDO was exhibited by the Ni/Cmicro (49.2 %) and
Ni/MMC-X (> 76 %) catalysts respectively. The ratio between the
meso- and macroporosity in the Ni/MMC-X catalysts did not appear
to have an effect on the PDO selectivity (~77 %), but was notably
higher than the PDO selectivity observed over the mesoporous
Figure 2 Stability tests of 12.5% Ni/MMC-1 catalyst for the glycerol
hydrogenolysis. The pentangle () denotes the specificity coefficent
towards hydrogenation to 1,2-propanediol (α). Herein, PDO (1,2-
propanediol), LA (lactic acid), EG (ethylene glycol).
The stability of the Ni/MMC-1 catalyst over sequential runs was
also investigated and the results from these experiments are
displayed in Figure 2 and Table 1. The catalyst was determined to be
stable up to at least 4 uses, and only a minor drop in the glycerol
conversion and PDO selectivity was observed. This slight drop in
activity is likely to be attributed to a reduction in the total surface
area of the catalyst, which was determined by BET characterization
3
Ni/MC (71 %). The selectivity to C products (PDO and LA) was
comparable for all the hierarchical catalysts (Ni/MC and Ni/MMC-
X) which were tested (~90 %), while the Ni/Cmicro exhibited a lower
C
3
selectivity of 73%. Only trace quantities of by-products
emanating from further degradation were observed. Interestingly,
the ratio between LA and PDO produced over the different catalysts
varied quite significantly. As discussed previously, LA is produced
by the rearrangement reaction from PA, the reaction of which
competes directly with the hydrogenation of PA/HAto produce PDO.
Given that higher PDO selectivity is observed with the Ni/MMC-X
catalysts, it indicates that these catalysts are likely to be more
efficient hydrogenation catalysts than the other catalysts
investigated. In order to quantify this trend, we have proposed a
specificity coefficient (α), defined below:
th
of the catalyst after a 5 consecutive reaction (Table S2). To verify
that this slight deactivation was not attributed to the leaching of Ni
species, ICP-OES analysis was conducted on the post-reaction
effluent after a standard reaction (210 °C, 6 h) with Ni/MMC-1; only
trace quantities (< 0.2 ppm) of Ni were observed (< 0.8 wt% of initial
Ni loading), indicating the small deactivation is not likely to be a
result of Ni leaching.
Origin of the improved hydrogenation activity
Selectivity1,2−PDO
ꢀ
=
(1)
Reactants and products can readily enter and exit micropores,
but usually experience diffusional effects as a consequence. This
diffusional limitation will undoubtedly be reduced in the Ni/MMC-
X catalysts, as the pore volumes associated with these materials are
significantly larger than those of the other conventional carbon
supports (Table S1). This would reduce any steric hindrance and
SelectivityLA
The α values for the reactions conducted over each of the
catalysts are displayed in Table 1. The Ni/MMC-X catalysts
exhibited α values between 5.8 – 6.1, which is approximately three
times higher than that exhibited by the Ni/Cmicro catalyst (2.1) and
approximately twice higher than that exhibited by the Ni/CNT and
Ni/MC catalysts; determined to be 3.4 and 3.9 respectively.
[
21]
mass transfer
across the catalyst and ultimately, improve
accessibility to and from the active sites (Ni metal sites or acid
[
33]
sites). This is one possible explanation as to why a higher reaction
activity and selectivity to PDO is observed with the Ni/MMC-X
catalysts. An increased accessibility to the Ni sites would likely lead
to an increased rate in the hydrogenation of HA(3) and PA(4). Given
that this hydrogenation reaction competes directly with the
rearrangement reaction, it can be used to rationalize why higher
selectivity to PDO is observed as the expense of LA.
In addition to enhancements in surface area and pore volume, it
was also important to consider how the hierarchical MMC materials
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First author et al.
[a]
Table 1 Aqueous-phase hydrogenolysis of glycerol over Ni-based carbon catalysts under alkaline conditions.
Carbon
balance
Carbon selectivity [%]
coefficient
specificity
of
Conversion
%]
[
b]
Entry
Catalyst
[
PDO
LA
EG
Ethanol
[
%]
α = SPDO / SLA
[
13]
1
2
3
4
5
6
Raney Ni
Ni/Cmicro
Ni/CNT
Ni/MC
Ni/MMC-1
Ni/MMC-6
Ni/MMC-
66.1
74.3
84.7
80.9
94.7
95.5
85.7
86.1
93.6
95.8
96.4
95.9
48.4
49.2
67.4
71.0
76.3
77.1
22.5
23.9
19.8
18.4
14.5
12.6
4.9
6.9
3.6
3.7
3.7
4.2
2.5
1.3
1.7
1.7
1.7
1.8
2.2
2.1
3.4
3.9
5.2
6.1
7
93.9
87.2
96.5
87.9
76.6
71.0
13.0
12.0
5.1
1.7
1.6
2.0
5.8
5.9
1
8
Ni/MMC-1
4 run)
:
8
th
(
Ni/MMC-
th
9
1(4
run+
90.0
92.9
72.0
15.1
3.1
1.9
4.8
[
c]
reduced)
Reaction conditions: 12.5 wt.% Ni loading, 20 wt.% glycerol, 0.5 M NaOH, wt % (substrate/catalyst) = 8, p (H
[
a]
2
) = 4 MPa, 210 °C, 6 h. Herein,
PDO (1,2-propanediol), LA (lactic acid in form of lactate), EG (ethylene glycol).
[
b]
Others: methane, methanol, 1-propanol.
Ni/MMC-1 recycled after the 4th run was then reduced under hydrogen.
[
c]
affected the properties of the supported Ni nanoparticles. In order to
determine how the support materials affected the redox properties,
H -TPR experiments were conducted on the calcined catalysts prior
2
proportional to the quantity of mesopores present in the calcined
materials. The results from the TPR experiments clearly indicate that
the properties of the support material have a significant effect on the
to their reduction, see Figure 3. For each of the catalysts investigated, reducibility of the NiO nanoparticles.
there are two clear reduction peaks present. The peak at
approximately 272 °C can be assigned to the reduction of NiO
crystals over the macropores or on the external grains of the
2
H -TPD experiments were subsequently performed, the results
of which are displayed in Figure 3. A large desorption peak was
observed at approximately 70 °C with all of the materials. The
lowest desorption temperatures; exhibited by the hierarchical
catalysts (Ni/MMC and Ni/MC), indicates that the bond strength of
Ni-H is weaker than the other catalysts, hence the release of
hydrogen over Ni particles supported on MMC is more favorable.
This could be evidenced as to the greater hydrogenation activity, and
as a consequence to a greater PDO selectivity from the Ni-MMC
[
36]
material.
Interestingly, this peak shifts to a higher temperature
when an increased proportion of macropores were present in the
Ni/MMC-X materials. Assuming that this ascribes to an increased
quantity of large NiO particles present on the surface of the
macropores, based on the particle size distributions displayed in
Figure 1 and S2, we can conclude that the reducibility of the NiO
particles decreases as the particle size increases.
2
catalysts. From the H -TPR and H2-TPD experiments, we can
Another reduction peak is also observed with all the catalysts at
approximately 422 °C. Previous reports have indicated that this peak
is attributed to the reduction of NiO particles immobilized on the
conclude that the redox properties of the Ni catalysts are heavily
influenced by the porosity of the carbon support.
[
37]
external or internal surface of mesoporous carbon.
This aligns
with the results displayed in Figure 3, as the intensity of this peak is
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Chin. J. Chem.
2 2
Figure 3 H -TPR profiles for the Ni/MMC catalysts and H -TPD profiles for Ni/CNT, Ni/Cmicro and Ni/MMC catalysts.
silicas as the hard template.[34] HF (10 wt.% in H
ensure the complete removal of silica template.
O) was used to
2
Conclusions
Multiporous carbon supported Ni catalysts are highly active,
selective and stable catalysts for the hydrogenolysis of glycerol to
PDO. The high performance of these catalysts was predominantly
attributed to their high surface areas and pore volumes, which was
proposed to reduce mass transfer limitations in the system. The
macroporous component in these materials also influenced the
Preparation of 12.5 wt.% Ni/MMC catalysts
The Ni catalysts were prepared by an incipient wetness
[
41]
impregnation method.
immersed in a precursor solution containing Ni(NO
The support (MC and MMC-X) were
·6H O in de-
3
)
2
2
ionized water (10 mL). It was followed by vacuum drying at 120 °C
for 4 h. All catalysts were subsequently reduced under a flowing 5%
2
redox properties of the supported Ni nanoparticles. H -TPD
−
1
experiments revealed a downward shift in temperature for hydrogen
desorption in the Ni/MMC-X catalysts, which was postulated to be
a result of weaker Ni-H bond strengths. This study is an example of
how hierarchical support materials can be used to tailor catalytic
activity and selectivity in liquid phase reactions.
2
H /Ar at 300 °C for 2 h (5°C∙min ). The Ni loading (12.5 wt.% Ni)
was confirmed by ICP-OES method.
1.3 Catalyst characterization
Powder X-ray diffraction patterns were obtained using a Bruker
D8 Advance X-ray powder diffraction instrument with a Cu-Ka
radiation (k=0.154 nm, 40 kV and 10 mA,). The ICP-OES was
conduct on a ThermoiCAP 6300 spectrometer. Scanning electron
microscopy images were collected on a Philips XL-30. BET surface
Experimental
1
.1 Materials
areas were determined by N
2
adsorption-desorption experiments
Styrene (99%, TCI Co., Ltd.), divinylbenzene (80%, Aladdin
with a Micromeritics ASAP 2020. H temperature programmed
2
Co., Ltd.), potassium persulfate (99%, Aladdin Co., Ltd.),
Tetraethyl orthosilicate (TEOS, Si(OC₂H₅)₄ , Si O >28.5%),
polyethylene oxide–polypropylene oxide–polyethylene oxide (P123,
EO20PO70EO20, Mw 5800, Sigma-Aldrich Co., Ltd.),
Ni(NO ·6H O (A.R., Sinopharm Chemical Reagent Co., Ltd.),
glucose (98%, Aladdin Co., Ltd), glycerol (99%, Aladdin Co., Ltd).
reduction and desorption experiments were conducted on a
Micromeritics Autochem II 2920 chemisorption instrument.
2
In a H
2
-TPR experiment, catalyst (50~100 mg) was pretreated
O and other
=
in air at 150 °C for 1 h to remove physically adsorbed H
2
3
)
2
2
impurities. After cooling to room temperature, the sample was
flushed for 0.5 h and then heated to 850 °C at a heating rate of
-
1
3
-1
1
0 °C∙min with a flowing of 5% H
TPD experiment, catalyst (50~100 mg) was prereduced for 1 h in a
flowing 5% H /Ar. After cooling to room temperature, the sample
was flushed for 0.5 h and then heated to 850 °C at a rate of
2 2
/Ar (50 cm ∙min ). In a H -
1
.2 Catalyst preparation
2
Synthesis of macro-mesoporous carbon
-1
3
-1
Polystyrene spheres were first prepared by the method proposed
10 °C∙min with a flowing of Ar (50 cm ∙min ).
[
29, 38, 39]
by Vaudreuil et al.
Then macro-mesoporous SBA-15 silica
composite (MM-SBA15) were prepared via a dual-templating
1.4 Catalytic reaction
In a standard reaction, catalyst (0.05 g) was reduced in-situ
2
under H at 400 °C for 2 h at a heating rate of 5 °C min , and was
[
40]
route.
Finally, the macro-mesoporous carbon (MMC-X) was
-1
prepared by a modified nano-casting method, which utilized glucose
as the carbon precursor and the newly synthetic MM-SBA15-X
then transferred to a 50 mL Teflon-lined stainless-steel autoclave.
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First author et al.
To this, the reactant solutions (20 wt.% glycerol aqueous solution
[
2] Nations, U. Sustainable bioenergy: a framework for decision
(10 mL), base additives) were added and the autoclave was sealed.
makers. NU: 2007.
3] Ayoub, M.; Abdullah, A. Z. Critical review on the current
The reactor was then purged with H (2-3 MPa) three times and
2
finally pressurized (4.0 MPa). The reactor was subsequently heated
to 210 °C in the oil bath. Upon reaching the desired reaction
temperature, the reactor was stirred at 1200 rpm. The reaction was
maintained under these conditions for 6 h. Once the reaction was
complete, the reactor was cooled down to room temperature by
immersing the sealed reactor in icy water. Gas samples were
collected with a gas-bag.
[
scenario and significance of crude glycerol resulting from biodiesel
industry towards more sustainable renewable energy industry.
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2
686.
[4] Yin, H.; Zhang, C.; Yin, H.; Gao, D.; Shen, L.; Wang,
1
.5 Product analysis
Gas products (Methane) were analyzed by using GC with a
thermal conductivity detector (TCD; GC-8A, Shimadzu) equipped
with an active carbon column. The liquid-phase products formed in
A. J. C. E. J. Hydrothermal conversion of glycerol to lactic acid
catalyzed by Cu/hydroxyapatite, Cu/MgO, and Cu/ZrO2 and
the reaction were quantified by both HPLC and GC-FID (Lactic acid; reaction kinetics. 2016, 288, 332-343.
PDO, EG, EtOH trace amount of methanol and 1-propanol). The
[
5] Yin, H.; Yin, H.; Wang, A.; Shen, L.; Liu, Y.; Zheng,
liquid phase products (Shimadzu LC-20AB) attached with a
refractive index detector (RI, Shimadzu RID 10A) and an Aminex
HPX-87H column (Bio-Rad, 300×7.8 mm). An aqueous mobile
phase containing sulphuric acid (0.005 M) was used at a flow rate
Y. J. J. o. n.; nanotechnology Catalytic conversion of glycerol to
lactic acid over metallic copper nanoparticles and reaction kinetics.
2017, 17 (2), 1255-1266.
-1
of 0.7 mL∙min . The column temperature was maintained at 60 °C
throughout the analysis procedure. The GC-FID was equipped with
a polyethylene glycol (PEG) column (20 m × 0.25 μm × 0.25 mm;
Dalian Zhonghuida Co., Ltd, China). The carbon balance was
defined as the percentage of carbon accounted for in the liquid phase
after 6 h reaction. The conversion of glycerol was calculated by
measuring the amount of glycerol before and after the reaction. The
selectivity was calculated by comparing the moles of carbon in the
specific product by the moles of carbon in consumed glycerol.
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The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
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Iborra, S.; Corma, A. Synthesis of
#
These authors contributed equally to this work.
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Acknowledgement
The authors gratefully acknowledge the support of Boya
Postdoctoral Fellowship of Peking University, prof. Graham J.
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Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
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Running title
Chin. J. Chem.
Entry for the Table of Contents
Page No.
Multiporous
Carbon
Encapsulated
Ni
Nanoparticles Promote Glycerol Valorisation
towards Hydrogenation against Rearrangement
Ni-based multiporous carbon catalysts containing macropores (~200 nm) and mesoporous channels
(
~4 nm) are highly selective and stable for glycerol conversion towards the hydrogenation to 1,2-
Bin Zhang, Bin Chen, Mark Douthwaite, Lipeng
Tang, Yibo Zhang, Meng Wang, Ding Ma*
propanediol against rearrangement to lactic acid in alkaline condition.
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
This article is protected by copyright. All rights reserved.