Effective Hydrogenolysis of Glycerol to 1,3-Propanediol over Metal-Acid Concerted Pt/WOx/Al2O3 Catalysts

Article abstract of DOI:10.1002/cctc.201900689

Selective cleavage of secondary C?O bond is an important yet challenging strategy in glycerol valorization, and the product 1,3-propanediol (1,3-PDO) is of great value in polyester industry. Herein, we report a series of Pt/WO_x/Al₂O₃ catalysts for selective hydrogenolysis of glycerol in a fixed-bed reactor and obtain the highest space-time yield of 1,3-PDO (191.7*10^?3 g_1,3-PDO h^?1 g^?1 _cat.) to date. Both Pt and W have substantial effects on the 1,3-PDO yield with the optimum Pt/W atomic ratio of 1/2～1/4. Spectroscopy characterizations as well as chemisorption experiments reveal that at the medium domain size of WO_x, hydrogen spillover can take place to the greatest extent due to the improved dispersion of Pt and the suitable reducibility of WO_x. Dehydration/dehydrogenation tests of 2-butanol suggest that strong Br?nsted acid sites are created via hydrogen dissociation at the Pt?WO_x interface and spillover to the neighboring oxygen atom. Such in situ formed protons are critical to the selective cleavage of secondary C?O bonds of polyols.

Full text of DOI:10.1002/cctc.201900689

Accepted Article
Title: Effective Hydrogenolysis of Glycerol to 1,3-Propanediol over
Metal-Acid Concerted Pt/WOx/Al2O3 Catalysts
Authors: Nian Lei, Xiaochen Zhao, Baolin Hou, Man Yang, Maoxiang
Zhou, Fei Liu, Aiqin Wang, and Tao Zhang
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10.1002/cctc.201900689
ChemCatChem
FULL PAPER
Effective Hydrogenolysis of Glycerol to 1,3-Propanediol over
Metal-Acid Concerted Pt/WOx/Al2O3 Catalysts
†
†
Nian Lei,[a,b] Xiaochen Zhao,[a] Baolin Hou,[a] Man Yang,[a,b] Maoxiang Zhou,[a,b] Fei Liu,[a]
Aiqin Wang,*[a] Tao Zhang[a]
Abstract: Selective cleavage of secondary C-O bond is an important
yet challenging strategy in glycerol valorization, and the product 1,3-
propanediol (1,3-PDO) is of great value in polyester industry. Herein,
2,000 $) and it is widely used as the monomer for production of
PTT (polytrimethylene terephthalate), a high-quality polyester.[8]
Therefore, the selective hydrogenolysis of glycerol to 1,3-PDO is
highly desirable yet more challenging. Driven by the great
potential for practical applications, this reaction has been
intensively studied.[9-57] So far, it has been established that a
noble metal in combination with an oxophilic metal oxide,
we report
a series of Pt/WOx/Al2O3 catalysts for selective
hydrogenolysis of glycerol in a fixed-bed reactor and obtain the
highest space-time yield of 1,3-PDO (191.7*10-3 g1,3-PDO h-1 g-1cat.) to
date. Both Pt and W have substantial effects on the 1,3-PDO yield
with the optimum Pt/W atomic ratio of 1/2~1/4. Spectroscopy
characterizations as well as chemisorption experiments reveal that
at the medium domain size of WOx, hydrogen spillover can take
place to the greatest extent due to the improved dispersion of Pt and
the suitable reducibility of WOx. Dehydration/dehydrogenation tests
of 2-butanol suggest that strong Brønsted acid sites are created via
hydrogen dissociation at the Pt-WOx interface and spillover to the
neighboring oxygen atom. Such in situ formed protons are critical to
the selective cleavage of secondary C-O bonds of polyols.
typically like Ir-ReOx[9-22] Rh-ReOx[23-24] and Pt-WOx[25-56], is
,
effective for the formation of 1,3-PDO. In comparison with ReOx,
WOx offers the advantage of better leaching-resistance and
lower cost, therefore shows greater potential for practical
applications. In an early report by Chaminand et al.,[25] it was
found that the addition of tungstic acid to rhodium catalysts in a
polar aprotic solvent sulfolane resulted in an increase of 1,3-
PDO selectivity although the overall yield of 1,3-PDO was lower
than 5%. Later, Kurosaka et al. improved the yield of 1,3-PDO to
24% by employing Pt/WO3/ZrO2 as the catalyst and DMI (1,3-
dimethyl-2-imidazolidinone) as the solvent.[26] Similar to the
Pt/WO3/ZrO2 catalyst, when Pt was deposited on sulfated
zirconia, the resulting catalyst showed a high selectivity for 1,3-
PDO in DMI solvent, and the 1,3-PDO yield reached as high as
55.6% after reaction at 170 oC and 7.3 MPa for 24 h.[57] However,
in the above studies, organic solvents were used and played
somehow a key role in the selectivity control.[58] From both
economic and environmental point of view, water as the solvent
would be highly desirable. When the reaction was carried out in
aqueous phase, the hydrothermal stability of the catalyst must
be considered. Zhu and coworkers studied the reaction in
aqueous phase using a continuous fixed-bed reactor system.
They initially used ZrO2 supporting Pt-silicotungstic acid (HSiW)
as the catalyst, and observed significant leaching of the HSiW
species resulting in activity loss during the reaction. To improve
the water tolerance of the catalyst, they then modified the
catalyst with alkali metals and achieved good stability over Pt-
LiSiW/ZrO2 catalyst during 120 h time-on-stream meanwhile
remaining high yield of 1,3-PDO (23.3 %).[27] In comparison with
the water-soluble heteropolyacids, WO3 is apparently more
resistant to leaching. Qin et al. investigated the reaction over
Pt/WO3/ZrO2 catalyst in a continuous fixed bed reactor system
under mild reaction conditions (130 oC, 4 MPa H2), and obtained
1,3-PDO yield of 32.0%.[28] However, using the same catalyst
Gong et al. obtained an 1,3-PDO yield of only 6.3%.[29] Zhu et al.
reported that the use of mixed oxides SiO2-ZrO2 could facilitate
the dispersion of WO3 and Pt and thus improved the activity and
selectivity; the 1,3-PDO selectivity arrived at 52.0% at 54.3%
conversion of glycerol.[30] Using Pt/WO3/TiO2/SiO2 as the catalyst,
Gong et al. obtained a high selectivity of 1,3-PDO (50.5% at
15.3 % glycerol conversion) after reaction at 180 oC and 5.5
MPa H2 for 12 h, and they also found that the presence of TiO2
was beneficial to the dispersion of Pt and WO3.[31] In various
oxide-supported Pt/WOx catalyst systems, Pt/WOx/AlOOH which
Introduction
With the immense consumption of fossil resources, there are
ever increasing concerns on the environmental issues such as
greenhouse gas emissions and smoggy air. To alleviate the
pressure on the environment, researchers are exploring the
carbon-neutron biomass for the sustainable production of fuels
and chemicals.[1] Glycerol, one of the top twelve biomass-
derived platform molecules, is available at large scale and low
cost as a byproduct in biodiesel production.[2] The valorization of
glycerol is not only able to improve the economic competition of
the biodiesel, but also able to contribute to the sustainability of
the involved chemistry.[3-4]
Hydrogenolysis of glycerol to diols is one of the most
important approaches to valorization.[5] The product selectivity is
critically dependent on the catalyst composition and structure.
For most transition metal catalysts supported on conventional
oxides, such as Cu and Ru on silica,[6] the main product is 1,2-
propanediol (1,2-PDO) as it is thermodynamically favorable.[7] In
contrast to 1,2-PDO, 1,3-PDO is more valuable (5,000 $ vs.
[a]
Nian Lei, Xiaochen Zhao, Baolin Hou, Man Yang, Maoxiang Zhou,
Fei Liu, Prof. Aiqin Wang, Prof. Tao Zhang
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Dalian 116023, China
E-mail: aqwang@dicp.ac.cn
[b]
Nian Lei, Man Yang, Maoxiang Zhou
University of Chinese Academy of Sciences
Beijing, 100049, China
†
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201900689
ChemCatChem
FULL PAPER
was first reported by Kaneda and coworkers,[32] appeared as the
most promising one. Under the reaction condition of 180 oC, 5
MPa H2 and 12 h, the selectivity of 1,3-PDO reached 66% with
complete conversion of glycerol. The authors attributed the
superior performance to the abundant hydroxyl groups of the
boehmite support. However, the catalyst precursor was calcined
hydrogenolysis of glycerol at a relatively high glycerol feed
concentration (50 wt%), and the results are shown in Table 1.
First, we investigated the effect of W loading at a constant Pt
loading. When the Pt content was fixed at 2 wt%, both the
glycerol conversion and the 1,3-PDO selectivity increased with
the W loading, and the highest 1,3-PDO yield of 15.1% was
obtained at the W loading of 7.5 wt%. Further increasing the W
loading resulted in decrease of both glycerol conversion and 1,3-
PDO selectivity. Similarly, when the Pt loading was kept at 4
wt%, increasing the W loading from 7.5 wt% to 12.9 wt% led to a
remarkable increase of the glycerol conversion from 29.7% to
62.7%, together with a slight decrease of the 1,3-PDO selectivity.
Further increasing the W loading to 20.4 wt% resulted in decline
in both the glycerol conversion and 1,3-PDO selectivity. Clearly,
the 1,3-PDO yield showed a volcano-shaped dependence on the
W loading at each Pt content, and a higher W loading required a
higher Pt loading to match it. On the other hand, when the W
loading was fixed at 12.9 wt%, increasing the Pt loading from
1% to 6 wt% could bring about a proportional increase of the
glycerol conversion, suggesting that the Pt dispersion remain
constant within this range of Pt loading. However, further
increase of the Pt loading to 8 wt% resulted in significant
decrease of the glycerol conversion due to the decrease of the
Pt dispersion. Meanwhile, the 1,3-PDO selectivity slightly
decreased with an increase of the glycerol conversion, which
was caused by the over-hydrogenolysis of glycerol to 1-PO. We
also investigated the effect of Pt at other fixed W loadings, e.g.,
7.5 % and 20.4 wt%, and observed similar trends. In terms of
1,3-PDO yield, the 6Pt/12.9W/Al2O3 was among the most active
and selective catalysts, which afforded the 1,3-PDO yield of
28.4%.
o
at 800 C prior to the reaction, which implied that the boehmite
was probably transformed into γ-Al2O3 and that the hydroxyl
groups on the surface might not be so important as the authors
proposed. Following the work, García-Fernández et al.
investigated the catalytic performance of Pt/WOx/Al2O3 catalyst
and obtained 1,3-PDO selectivity of 51.9% at 53.1% glycerol
conversion when the Pt content was as high as 9 wt%.[33] Such a
high content of Pt would make the catalyst very expensive and
thereby limit the practical applications. Zhu et al. also
investigated the catalytic performance of Pt/WOx/Al2O3 using a
continuous fixed-bed reactor system, and obtained 1,3-PDO
yield of 42.4% when Pt and W contents were 2 wt% and 10 wt%,
respectively.[34]
In spite of intensive studies, a clear image of the reaction
mechanism as well as the exact active sites is still lacking.
Tomishige and coworkers proposed that the reaction over the Ir-
ReOx proceeded via a direct hydride-proton mechanism by
forming relatively stable 6-membered-ring intermediate at the
interface of Ir-ReOx.[10] Zhu et al. assumed that Brønsted acid
sites on the support surface were responsible for the 1,3-PDO
formation, while Lewis acid sites favored the 1,2-PDO
formation.[34] However, that claim could not explain why glycerol
was not converted at all in the absence of H2 or Pt/Ir under
otherwise identical conditions. Therefore, the discussion of
acidity independently without concerning the contribution of
noble metal species is unreasonable. In other words, the concert
and balance between noble metal (Pt/Ir) and oxophilic oxides
(WOx/ReOx)
is
paramount
for
the
chemoselective
hydrogenolysis.[59] However, the complexity in preparation and
the close atomic numbers between the oxophilic element and
noble metal render the structure identification rather challenging,
thus limit the mechanistic understanding of supported Pt-W or Ir-
Re catalysts as well as the rational design of catalysts.
In this contribution, we prepared a series of Pt/WOx/Al2O3
catalysts and evaluated them for the selective hydrogenolysis of
glycerol in a fixed-bed reactor and under relatively high glycerol
concentration (50 wt%). Under the optimized Pt/W ratio and
reaction conditions, we have obtained the highest 1,3-PDO
productivity to date (191.7*10-3 g1,3-PDO h-1 g-1cat.) over the
6Pt/12.9W/Al2O3 catalyst. By using various characterization
techniques and dehydration/dehydrogenation of 2-butanol as the
probe reactions, we have for the first time provided strong
evidence that the in situ formed Brønsted acid sites via
dissociation of H2 at the Pt-WOx interface and spillover of H
atom to the WOx surface were responsible for the high 1,3-PDO
yield.
Results and Discussion
Figure 1. Contours showing the glycerol conversion (a) and 1,3-PDO yield (b)
The series of Pt/WOx/Al2O3 catalysts were evaluated for the
as functions of W and Pt loadings.
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Table 1. Selective hydrogenolysis of glycerol over Pt/WOx/Al2O3 catalysts.[a]
Selectivity (%)
Conversion
1,3-PDO
Yield (%)
Entry
Catalyst
1,3-PDO
0
1,2-PDO
100.0
22.9
13.3
14.0
9.9
1-PO
0
2-PO
0
Others[b]
0
(%)
1
2
2Pt/Al2O3
trace
10.8
22.2
15.9
31.2
29.7
34.0
14.6
22.9
46.5
62.7
70.1
80.4
57.7
20.1
43.1
57.2
13.4
0
2Pt/1.0W/Al2O3
2Pt/4.0W/Al2O3
1Pt/7.5W/Al2O3
2Pt/7.5W/Al2O3
4Pt/7.5W/Al2O3
6Pt/7.5W/Al2O3
1Pt/12.9W/Al2O3
2Pt/12.9W/Al2O3
3Pt/12.9W/Al2O3
4Pt/12.9W/Al2O3
5Pt/12.9W/Al2O3
6Pt/12.9W/Al2O3
8Pt/12.9W/Al2O3
2Pt/20.4W/Al2O3
4Pt/20.4W/Al2O3
6Pt/20.4W/Al2O3
2Pt/30.8W/Al2O3
37.7
42.8
46.2
48.5
43.5
43.3
44.1
44.8
38.3
39.4
39.5
35.3
43.5
38.0
36.2
37.3
38.1
23.4
24.6
25.9
29.6
28.0
29.8
24.8
26.0
31.7
36.3
38.9
41.8
35.5
29.6
33.7
35.6
35.6
5.9
10.1
11.5
5.9
4.1
3
7.7
9.5
4
8.0
7.3
5
10.7
10.1
9.9
1.3
15.1
12.9
14.7
7.0
6
10.0
9.5
8.4
7
7.5
8
17.2
16.8
13.1
9.8
10.3
10.3
11.1
12.2
13.0
12.3
11.5
10.3
10.9
11.6
9.7
3.6
9
2.1
10.2
17.8
24.7
27.7
28.4
26.1
7.6
10
11
12
13
14
15
16
17
18
5.8
2.3
7.2
1.4
4.9
5.7
7.0
2.5
13.4
10.4
8.9
8.7
8.8
15.6
21.3
5.1
6.6
14.6
2.0
[a] Reaction conditions: 180 oC, H2 (5.0 MPa), 50 wt% GLY, GHSV = 1000 h-1, LHSV = 1.0 h-1.
[b] Others include propane, ethylene glycol, ethanol, methanol, methane and ethane.
Based on the data in Table 1, one can see that the effects of
Pt and W loadings on the selective hydrogenolysis of glycerol to
1,3-PDO are interdependent, which can be illustrated as
contours in Fig. 1. Considering both the yield of 1,3-PDO and
the cost of catalyst, moderate Pt loading (e.g., 5 wt%) and
medium W loadings (10~15 wt%) are favorable, and the suitable
Pt/W atomic ratio is in the range of 1/2~1/4.
In addition to the catalyst composition, the reaction conditions
also imposed impacts on the glycerol conversion and 1,3-PDO
selectivity. As shown in Fig. S1, the glycerol conversion
monotonically increased with the reaction temperature and
hydrogen pressure, whereas the 1,3-PDO selectivity decreased
dramatically with the rise of temperature due to over-
hydrogenolysis to 1-PO, suggesting that lower temperature
favors the formation of 1,3-PDO. Differently, the hydrogen
pressure showed a positive effect on the 1,3-PDO yield. Liquid
hourly space velocity (LHSV) and gas hourly space velocity
(GHSV) were also investigated. Following the general feature of
consecutive reactions, higher LHSV favored 1,3-PDO selectivity
but caused decrease of the glycerol conversion. On the other
hand, GHSV in the range of 1000~4000 h-1 had a negligible
effect on the catalyst performance, suggesting that gas to liquid
mass transfer was no longer a limiting factor when the GHSV
was larger than 1000 h-1.
times of the second best catalyst Ce-Pt/WO3/TiO2-SiO2 (69.0*10-
3 h-1).[60] When counting batch catalytic systems into comparison,
the performance of the 6Pt/12.9W/Al2O3 catalyst is still
distinguished and next only to the Ir-ReOx/SiO2 catalyst,[9] whose
component may be easily leached and hence unfeasible in
fixed-bed reactor systems.
In order to understand the interdependent effects of Pt and W
loadings on the catalyst performance and further to establish the
structure-performance relationship, we conducted extensive
characterizations of the series of Pt/WOx/Al2O3 catalysts.
Fig. 2 shows XRD patterns of the series of Pt/WOx/Al2O3
catalysts. The crystalline WO3 was not detected until the W
loading was above 20.4 wt% (Fig. 2a), indicating that the WOx
species were dispersed as sub-monolayer when its loadings on
the Al2O3 support were below 20.4 wt%. In good agreement with
the XRD results, the ν (O–W–O) modes (714 cm-1 and 807 cm-1)
which were assigned to bridging oxygen of WO6 octahedra,[61]
appeared only when the W loading was above 20.4 wt% in the
Raman spectra (Fig. 3a). In contrast, only the stretching mode of
the distorted terminal W=O bond (959~989 cm-1) was observed
on the samples with W loading below 20.4 wt%. Moreover, this
W=O vibration band shifted to lower wavenumbers and was
broadened with reduction of the W loadings, suggesting the
enhanced interaction of WOx with Al2O3 surface and its
decreased particle size.[62] Therefore, high W loading (> 20.4%)
catalysts are likely to demonstrate the characteristics of bulk
WO3; while low to medium W loading WOx catalysts display
Under the optimized reaction conditions, the highest space-
time yield of 1,3-PDO (191.7*10-3 h-1) reported so far in the fixed-
bed reaction systems (Table S1) was achieved, almost three
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10.1002/cctc.201900689
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distinctive chemistry. On the other hand, obvious diffraction peak
of Pt was observed on the 4Pt/7.5W/Al2O3, while it did not
emerge until the Pt loading increased to 8 wt% when the W
loading was 12.9 wt% (Fig. 2b). This result suggested that
submonolayer polytungstates are favorable for Pt dispersion,
which is consistent with the activity results (Table 1).
Figure 3. Raman spectra of the calcined WO3/Al2O3 (a) and reduced
Pt/WOx/Al2O3 (b) catalysts.
Figure 2. XRD patterns of the reduced Pt/Al2O3 and Pt/WOx/Al2O3 catalysts
with different W loading (a) and Pt loading (b).
Comparing the Raman spectra of WO3/Al2O3 catalysts with
and without platinum (Fig. 3a and 3b), one could see that the
loading of Pt caused a shift of the vibrational band (W=O) from
959 cm-1 to 1004 cm-1, accompanied by a slight increase in
intensity. This shift of Raman band was supposed due to the
interaction between platinum and surface tungsten oxides,
resulting in the distortion of oxotungsten species.[63] It should be
noted that the W=O band shift of Pt/WOx/Al2O3 (1004 to 1024
cm-1) followed the same trend as that of WO3/Al2O3 (959 to 989
cm-1) with the variation of W loadings, which suggests that the
structure of the WOx species is mainly determined by its surface
density, irrespective of the loading of Pt.
To further clarify the structure of WOx species, UV-vis, XPS,
N2 adsorption and ICP were conducted. In Fig. 4a, a gradual
decrease of edge energy (Eg) with high transmittance was
observed in the UV-vis diffuse reflectance spectra of WO3/Al2O3,
suggesting the electronic properties of WOx substantially
changed as the W loading increased. According to
Figure 4. (a) Electronic edge values based on UV-vis spectra of the calcined
WO3/Al2O3 samples and (b) Surface atomic ratio ((W/Al)XPS) as a function of
bulk atomic ratio ((W/Al)Bulk). The red dash line corresponds to Kerkhof-Moulijn
model.
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previous study[64] as well as XRD and Raman results, when the
W loading was ca. 1-4 wt%, WOx species were more likely to
disperse as monotungstate (Eg > 4.4 eV) (Table 2). As the W
loading was increased to 7.5 wt% and 12.9 wt%, both mono-
and polytungstates coexitsted (4.4 eV > Eg > 4.0 eV). With a
further increase of the W loading, the WOx species consequently
changed from polytungstates over the 20.4W/Al2O3 sample (Eg <
4.0 eV, W density < 4.5 W/nm2 (monolayer W coverage)[65]) to
3D nanocluster WO3 species over the 30.8W/Al2O3 and
40.0W/Al2O3 samples. This could be further validated by the
catalysts.[67] The H2 uptakes followed the same trend with CO
chemisorption, however, the dispersion of Pt based on H2
chemisorption was significantly higher than that based on CO
chemisorption, indicating that hydrogen spillover occurred on the
Pt/WOx/Al2O3 catalysts.[67-69] Moreover, the degree of hydrogen
spillover, which could be estimated from the difference between
Pt dispersionCO and Pt dispersionH , was found to strongly
2
depend on the interaction between Pt and WOx and became the
most pronounced on the 2Pt/7.5W/Al2O3 catalyst. Coincidently,
this catalyst gave the highest 1,3-PDO yield among the series of
Kerkhof-Moulijn (K-M) model in Fig. 4b. At W loading > 20.4 wt%, catalysts.
a deviation from monolayer deposition occurred.[66] It could thus
be concluded that the sub-monolayer WOx was formed on the
Table 3. CO/H2 chemisorption results of Pt/WOx/Al2O3 catalysts.
Al2O3 surface when the W loading was below 20.4 wt%. It is
noted that this threshold is much higher than that earlier
reported (9 wt%).[33] The higher threshold obtained in this work
might be due to the vacuum impregnation procedure as well as
the favorable textural properties of the Al2O3 support.
Uptake (μmol/g)
Dispersion (%)
Particle size (nm)
Catalyst
[b]
[c]
[d]
CO
57.2
51.4
52.6
53.4
56.6
16.4
10.4
7.7
H2
CO[a]
55.8
50.1
51.3
52.1
55.2
16.0
10.1
7.5
H2
dCO
dSTEM
2Pt/Al2O3
32.3
31.0
37.7
44.3
34.2
19.6
9.7
63.0
60.5
73.5
86.4
66.7
38.2
18.9
11.5
2.0
2.3
1.6±0.4
1.2±0.3
--
2Pt/1.0W/Al2O3
2Pt/4.0W/Al2O3
2Pt/7.5W/Al2O3
2Pt/12.9W/Al2O3
2Pt/20.4W/Al2O3
2Pt/30.8W/Al2O3
2Pt/40.0W/Al2O3
2.2
Table 2. Structure identification of WO3 in different WO3/Al2O3 samples.
2.2
1.1±0.4
--
2.0
Eg
(eV)
SABET
W density
(W/nm2)
Sample
Structure of W species
monotungstate
(m2g−1
)
7.1
1.7±0.4
--
1.0W/Al2O3
4.0W/Al2O3
7.5W/Al2O3
12.9W/Al2O3
20.4W/Al2O3
30.8W/Al2O3
40.0W/Al2O3
4.4
4.4
4.3
4.1
3.8
3.6
3.3
185.7
190.2
187.9
190.1
168.6
150.1
135.8
0.2
0.7
1.3
2.2
4.0
6.7
9.8
11.1
15.0
5.9
2.3±0.7
[a] Determined by CO uptake based on CO/Pt = 1.
[b] Determined by H2 uptake based on H2/Pt = 2.
[c] Determined by the equation: dCO = 1.13 / DispersionCO
[d] Determined by STEM.
combination of mono-
and polytungstates
[70]
.
polytungstates
nanocluster
Fig. 5 shows the HAADF-STEM images and particle size
distributions. Among the four WO3/Al2O3 samples, the
1.0W/Al2O3 sample (Fig. 5a) does not present any discernable
nanoparticles, suggesting the WO3 probably exists as isolated
monomer.[71] On the other hand, both the 7.5W/Al2O3 and
20.4W/Al2O3 samples show highly dispersed WO3 domains (Fig.
5c, e), and the poor contrast suggests the 2D structure of the
WO3 domains. In contrast, the obviously improved intensity of
the WO3 domains in the 40.0W/Al2O3 sample (Fig. 5g) strongly
suggests that the WO3 domains exist as 3D nanoparticles with
an average size of 1.4 nm. This result is consistent with the
above XRD, Raman, and UV-vis characterizations. After loading
of Pt, the image contrast for low- to medium-W-loading catalysts
(Fig. 5b, d) became much improved although the average
particle sizes did not change much. This result suggests that
most of the Pt particles probably reside on the WO3 domains
rather than on the alumina support. For the high-W-loading
catalysts (2Pt/20.4W/Al2O3 and 2Pt/40.0W/Al2O3), the average
Pt particle sizes were still below 3 nm although some bigger
particles were occasionally observed (Fig. 5f, h). Such small
sizes of Pt do not accord with the rather low CO and H2 uptakes
on these two samples, corroborating that strong metal support
interaction (SMSI) occurred during the reduction treatment,
which caused the partial encapsulation of Pt particles by the
WOx species.[67-68] This was further verified by the XPS Pt 4d
spectra, in which the intensity of surface Pt gradually decreased
when the W loading was increased, indicating less exposed Pt
species (Fig. S2).
As illustrated in Fig. 1, volcano profiles of glycerol conversion
and 1,3-PDO yield were obtained as functions of both W and Pt
loadings, and the optimized glycerol yield (~ 29%) could be
obtained when Pt loading was ca. 5.0~7.0 wt% and W loading
was ca. 11.0~17.0 wt% (1.9~2.9 W/nm2), although with a little
deviation. At this point, on the premise of highly dispersed Pt
species, when monotungstate and polytungstates coexisted, the
highest 1,3-PDO yield could be obtained.
The chemisorption of CO and H2 was conducted on the series
of Pt/WOx/Al2O3 catalysts with a constant Pt loading of 2 wt%
and various W loadings. As shown in Table 3, the CO uptakes
increased only slightly when the W loading increased from 1
wt% to 12.9 wt%, correspondingly, the dispersion of Pt was
slightly enhanced from 50.1% to 55.2%, which was close to that
of Pt/Al2O3. However, at a higher W loading (≥ 20.4 wt%), the Pt
dispersion was dramatically decreased to around 10%. This
result indicated that the Al2O3-supported 2D sub-monolayer WOx
was beneficial to the Pt dispersion, while monolayer or 3D WOx
cluster led to strong interaction with Pt and partially covering the
Pt sites upon H2-reduction, which eventually caused dramatic
decrease of CO uptakes. The mean particle size estimated from
STEM was markedly smaller than that estimated from CO
chemisorption for the high-W loading samples, approving that
the Pt surface was overcoated with WOx in these sample. The
similar phenomenon was also observed on Pt/WOx/TiO2
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Figure 5. HAADF-STEM images of (a) 1.0W/Al2O3, (b) 2Pt/1.0W/Al2O3, (c) 7.5W/Al2O3, (d) 2Pt/7.5W/Al2O3, (e) 20.4W/Al2O3, (f) 2Pt/20.4W/Al2O3, (g) 40.0W/Al2O3,
(h) 2Pt/40.0W/Al2O3.
CO adsorbed on isolated or positively charged Pt sites,[72-73]
while the bands at 1829-1848 cm-1 are due to the CO bridgedly
adsorbed on contiguous Pt sites.[74] On the other hand, the
bands at 2068-2085 cm-1 are asymmetric and can be
deconvoluted into three symmetric bands centred at 2070-2081
cm-1, 2029-2049 cm-1 and 1986-2006 cm-1 (Fig. S3). The bands
at 2070-2081 cm-1 can be assigned to CO adsorbed on Pt sites
that are bonding with the WOx domain (interfacial sites at the Pt-
WOx interface), while the latter two bands can be assigned to the
typical linear adsorption of CO on Pt nanoparticles with different
sizes.[75-76] It is interesting to note that with an increase of the W
loading, the CO absorption band at the Pt-WOx interface had a
blue shift, indicating that electron transfer from Pt to W occurred.
Moreover, the intensity of this band first increased with W
loading and reached the highest at the 2Pt/7.5W/Al2O3 catalyst,
then decreased with further increase of the W loading due to
SMSI. We plotted the intensity of CO absorption band of each
assignment as a function of W loading (Fig. S4) and found that
only the CO adsorption at the Pt-WOx interface changed in the
same manner as the 1,3-PDO yield did, as shown in Fig. 6b.
This result strongly suggests that the Pt-WOx interfacial sites are
catalytically active for the glycerol hydrogenolysis to 1,3-PDO.
In order to understand the key role of Pt-WOx interface, we
Figure 6. (a) DRIFT spectra of CO adsorbed on Pt/WOx/Al2O3 catalysts and (b)
probed the origin of acidity for the glycerol hydrogenolysis.
the relationship between CO-adsorbed IR intensity at the Pt-WOx interface and
Firstly, we performed NH3-TPD experiments to measure the
1,3-PDO yield.
permanent acid sites (not induced by H2) on the catalyst surface.
As shown in Fig. S5, the total amount of acid sites showed little
difference from 2Pt/Al2O3 (0.63 mmol NH3/gcat.) to 2Pt/WOx/Al2O3
To further understand the interaction between Pt and WOx,
(0.65-0.67 mmol NH3/gcat.
) while the strong acid amount
DRIFT spectra of adsorbed CO was performed to probe surface
Pt sites with different W loadings. As shown in Fig. 6a, CO
adsorption on the Pt/WOx/Al2O3 catalysts produced three
distinctive bands at 2122-2128 cm-1, 2068-2085 cm-1 and 1829-
1848 cm-1. The band at 2122-2128 cm-1 can be ascribed to the
increased steadily with the W content. However, the negligible
variance in the amount of permanent acids cannot account for
the large difference in the 1,3-PDO yield, thus the contribution of
the permanent acid sites on the WO3/Al2O3 surface can be
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10.1002/cctc.201900689
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precluded. Secondly, H2SO4 was introduced to the reaction
system to investigate the role of aqueous Brønsted acids playing
indicating the acidity of the catalyst governed the reaction while
the metallic nature was totally suppressed. This result is in good
in the selective hydrogenolysis of glycerol. As shown in Table S2, agreement with the DRIFTS, approving that higher W loading
both the glycerol conversion and the 1,3-PDO yield remained
substantially unchanged when the feed pH was adjusted from
6.6 to 4.3 by introduction of H2SO4, but they dramatically
dropped at lower pH conditions. This control experiment
confirmed that the introduction of strong liquid Brønsted acid did
not lead to the un-negligible improvement in the 1,3-PDO yield.
Since neither the solid surface acid sites nor the liquid acids
are responsible for the selective production of 1,3-PDO, the in-
situ generated Brønsted acids by dissociation and spillover of H2
should be considered as the main contributor. To approve this,
we used dehydration/dehydrogenation of 2-butanol under H2 and
N2 atmosphere as the probe reaction to investigate the acidity
produced by the dissociation and spillover of H2.[77-79] Because
both dehydration and dehydrogenation reactions can occur
depending on the acid/metal ratios, this reaction can also be
used to probe the bifunctionality of the catalysts.
resulted in SMSI and significantly reduced the exposed Pt sites.
On the other hand, when the reaction was conducted in H2, the
ratio of dehydration/dehydrogenation changed dramatically.
Except for the 2Pt/Al2O3 and 2Pt/4W/Al2O3 both of which still
showed dehydrogenation preference, all the other catalysts
demonstrated dehydration preference. In particular, for the
medium W loading catalysts (7.5 wt% W and 12.9 wt% W), the
product selectivity was totally reversed by the presence of H2,
that is, dehydrogenation products predominated in N2 while
dehydration product dominated in H2. Evidently, new acid sites
were formed by the presence of H2, possibly via hydrogen
dissociation and then spillover of H atom to the interfacial WOx
species, in accordance with previous reports.[67] Consequently,
the number of these new acid sites is critically dependent on the
cooperation of Pt and WOx, as revealed by the effect of Pt
loading at fixed W loading of 12.9 wt% (Fig. 7b). In the presence
of N2, these series of catalysts all showed dehydrogenation
capacities, whereas the presence of H2 made them all be
strongly acidic catalysts for the dehydration of 2-butanol, and the
number of acid sites reached maximum at the 6Pt/12.9W/Al2O3
catalyst. Coincidently, the best performance in terms of the 1,3-
PDO was also achieved with the same catalyst, strongly
suggesting that the newly created acid sites in the presence of
H2 were responsible for the selective hydrogenolysis of glycerol
to 1,3-PDO.
Combining all the experimental and characterization results,
we can postulate the reaction mechanism as below. The
[9-10, 33]
terminal OH of glycerol is protected by adsorption on WOx
while H2 is activated and dissociated into two H atoms at the
surface of Pt. Then, one H atom is spillover to the interfacial
WO3 site and reduce it to low-valence WOx and concurrently
form the Brønsted acid sites. When the polytungstates exist as
2D sub-monolayer with a medium domain size, the number of
Pt-WOx interface sites gets maximized due to highly dispersed
Pt and appropriate reducibility of the WOx, which favors the
hydrogen spillover and promotes the in situ formation of strong
Brønsted acid sites. The active protons then attack the
secondary carbon of glycerol, forming the secondary
carbocation intermediate, which could be hydrogenated by the
Pt-H at the Pt-WOx interface to form 1,3-PDO.
Figure 7. The conversion of 2-butanol in N2 or H2 over (a) 2Pt/WOx/Al2O3
catalysts with different W loading, and (b) Pt/12.9W/Al2O3 with different Pt
loading.
Conclusions
In summary, a series of Pt/WOx/Al2O3 catalysts were prepared
and evaluated for selective hydrogenolysis of glycerol to 1,3-
PDO in the fixed-bed reactor and under a relatively high glycerol
feed concentration. The catalytic performance was critically
dependent on the cooperation between Pt and WOx, and the
As shown in Fig. 7, when the reaction was conducted in N2,
the Pt/WOx/Al2O3 catalysts with the low to medium W loadings (<
20 wt%) mainly showed metallic nature by affording
dehydrogenation products, irrespective of the Pt loading. The
dehydrogenation activity can be well correlated with the CO
chemisorption data (Fig. S6), showing its dependence on the
exposed Pt sites. However, with an increase of the W loading,
the dehydration product gradually appeared and eventually
became predominant at the W loading greater than 20 wt%,
highest 1,3-PDO productivity to date (191.7*10-3 g1,3-PDO h-1 g-1
)
cat.
has been obtained on the 6Pt/12.9W/Al2O3 catalyst.
Spectroscopy characterizations suggested that the reaction
occurred at the Pt-WOx interface, which could promote the in situ
production of strong Brønsted acid sites through hydrogen
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10.1002/cctc.201900689
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HAADF-STEM images were obtained on a JEM-2100F Transmission
Electron Microscope operated at 200 kV and equipped with EDS
microanalysis system. The samples were prepared via ultrasonically
dispersing the calcined or reduced powers into ethanol solvent and
deposited on a holey C/Cu TEM grid.
dissociation and spillover. The number of Pt-WOx interfacial sites
was maximized at the medium domain size of WOx (7~15 wt%
W) due to the appropriate electronic interaction with Pt. This
mechanism understanding will help to guide the rational design
of more efficient catalysts for the selective cleavage of
secondary C-O bonds in a wide spectrum of biomass molecules,
which is of importance for sustainable chemistry.
UV–vis diffuse reflectance spectra (DRS) were obtained on a cintra (GBC)
apparatus equipped with an integrated sphere attachment with BaSO4 as
the reference. The samples were loaded into a sample cell and
measured in the region of 200–800 nm.
Experimental Section
CO chemisorption, H2 chemisorption, and Temperature-programmed
desorption of NH3 (NH3-TPD) were conducted on
a Micromeritics
Chemicals and materials
AutoChem II 2920 chemisorber. Prior to CO and H2 chemisorption
measurements, all the samples were pre-reduced at 300 oC under a
stream of pure H2 for 1 h, and then purged under inert gas (He for CO
chemisorption and Ar for H2 chemisorption) flow for 30 min at 310 oC.
After being cooled down to 50 oC, pulses of 5% CO/He or 10% H2/Ar
were introduced to the reactor for CO or H2 chemisorption until saturation
was reached. The consumed CO or H2 were detected with TCD and the
uptakes were calculated by calibration with the standard sample.
Glycerol, 1-propanol (1-PO), and 2-propanol (2-PO) were purchased
from Tianjin Kemiou Chemical Reagent Co., Ltd. 1,2-propanediol (1,2-
PDO) and n-butanol were purchased from Aladdin Chemistry Co., Ltd.
1,3-propanediol (1,3-PDO) was purchased from Acros chemicals co., Ltd.
Al2O3 was synthesized and pelletized in our laboratory. Ammonium
metatungstate (AMT) was purchased from Chenzhou Diamond Tungsten
Products Co., Ltd. H2PtCl6·6H2O was purchased from Tianjin Fengchuan
Chemical Reagent technology Co., Ltd. 2-butanol was purchased from
Sinopharm chemical reagent Co., Ltd.
In NH3-TPD measurement, the samples were pre-reduced at 300 oC
under a stream of pure H2 for 1 h, and then purged under He flow at 310
oC for 30 min. After that, the samples were cooled down to 100 oC for
NH3 adsorption. After adsorption saturation, the samples were heated
from 100 oC to 700 oC in He flow at a heating rate of 10 oC/min, while the
desorbed NH3 was monitored by a mass spectrometer system. In the
measurement, m/e = 16 was monitored to analyze the desorbed NH3 to
avoid the interference of water.
Catalyst preparation
Pt/WO3/Al2O3 catalysts were prepared by sequential impregnation
method. Specifically, Al2O3 was vacuum impregnated with an aqueous
solution of ammonium metatungstate (AMT), followed by drying at 110 oC
for 12 h and calcination at 700 oC for 3 h to obtain a series of yWO3/Al2O3
with different W contents (where y refers to the weight percent of W).
Then, the yWO3/Al2O3 samples were impregnated with an aqueous
solution of H2PtCl6·6H2O, followed by drying at 110 oC for 12 h and
calcination in static air at 300 oC for 3 h to obtain the xPt/yWO3/Al2O3
catalyts (where x refers to the weight percent of Pt). For comparison, a
Pt/Al2O3 sample was also prepared by the same procedure. The actual
contents of W and Pt of the catalysts were measured by inductively
coupled plasma atomic emission spectroscopy (ICP-AES). Prior to the
XRD, STEM, Raman and XPS characterizations, all the Pt/WOx/Al2O3
catalysts were reduced in flowing H2 at 300 oC for 1 h, and passivated
with 1% O2/N2 for 4 h at room temperature.
The X-ray photoelectron spectra (XPS) of reduced samples were
obtained on an ESCALAB 250 X-ray photoelectron spectrometer
equipped with monochromated Al Kα anode. All binding energies were
calibrated by referencing them to the energy of the C1s peak at 284.6 eV.
Diffuse reflectance infrared Fourier transform spectra (DRIFTS) were
recorded with a Bruker Equinox 55 spectrometer equipped with a
mercury cadmium telluride (MCT) detector at a resolution of 4 cm-1 using
128 scans. The sample was put into a cell, reduced at 300 oC under a
stream of pure H2 for 1 h and purged under He flow for 30 min at 310 oC.
After cooled down to 50 oC, background spectrum was recorded. After
that, 5% CO/He was introduced into the sample for 30 min. Pure He was
subsequently introduced to the cell to remove the physically adsorbed
CO, until the spectra of chemisorbed CO species were stable.
Catalyst characterization
Nitrogen adsorption-desorption measurements were performed at −196
oC on a Micromeritics ASAP 2460 instrument. The specific surface areas
(SBET) were calculated from the N2 adsorption isotherm with BET
equation, and the pore size distributions were obtained using desorption
branch of the isotherms and BJH method. Prior to the physisorption
measurements, the sample was firstly dehydrated at 110 oC for 1 h and
then degassed at 300 oC for at least 4 h.
Glycerol hydrogenolysis
The hydrogenolysis of glycerol was carried out in a fixed-bed down-flow
stainless steel reactor (length, 400 mm; internal diameter, 9.0 mm). The
catalyst (2.0 mL, 20–40 mesh) was positioned between two beds of
quartz sands. Prior to reaction, the catalyst was activated in flowing H2
(120 mL/min) at 300 oC for 1 h. After cooling down the reactor to reaction
temperature, aqueous solutions of glycerol were continuously pumped
into the fixed-bed reactor through a high-pressure liquid pump. Hydrogen
and glycerol solution flows were mixed at the inlet of the reactor. At the
reactor outlet, the liquid and gas flows were cooled and separated in the
The power X-ray diffraction (XRD) patterns were acquired on
a
PW3040/60 X’Pert PRO (PANalytical) diffractometer equipped with a Cu
Kα radiation source (λ= 0.15432 nm) operated at 40 kV and 40 mA. The
X-ray patterns of reduced samples were collected in the 2θ range from
10° to 80°.
o
gas-liquid separator. The standard reaction conditions were: 180 C, 5.0
MPa, 50 wt% glycerol aqueous solution, GHSV = 1000 h-1, LHSV = 1 h-1.
The effluent gas was analyzed online by Agilent 7890B GC with a
HayeSep Q packed column (3 m ×1/8", TCD detector ), while the liquid
was off-line analyzed by the same GC with an HP-INNO WAX capillary
column (30 m × 0.32 mm × 0.5 µm，FID detector) using n-butanol as
The Raman spectra were measured on a JobinYvon HR 800 Dispersive
Raman Spectrometer with a resolution better than 2 cm-1. The patterns of
calcined and reduced samples were collected in the 150–1500 cm-1
regions.
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Nian Lei, Xiaochen Zhao, Baolin Hou,
Man Yang, Maoxiang Zhou, Fei Liu,
Aiqin Wang,* and Tao Zhang
Page 1. – Page 11.
Effective Hydrogenolysis of
Glycerol to 1,3-Propanediol over
Metal-Acid Concerted Pt/WOx/Al2O3
Catalysts
The highest 1,3-PDO yield was obtained over the Pt/WOx/Al2O3 catalyst with a
medium domain size of WOx and a Pt/W atomic ratio of 1/4~1/2, which favored the
dispersion of Pt and maximized the number of Pt-WOx interface sites, and
consequently promoted the in-situ production of strong Brønsted acid sites.
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