Nanoparticulate Pt on mesoporous SBA-15 doped with extremely low amount of W as a highly selective catalyst for glycerol hydrogenolysis to 1,3-propanediol

Article abstract of DOI:10.1039/c7gc00317j

It has been documented that W-modified Pt catalysts with relatively high tungsten contents are effective for the catalytic transformation of biodiesel-derived glycerol to 1,3-propanediol (1,3-PDO). Herein, we report a new finding that Pt/W-SBA-15 catalysts with extremely low W/Si atomic ratios (≤1/80) exhibit excellent catalytic performance in the hydrogenolysis of glycerol to 1,3-PDO. In particular, a Pt/W-SBA-15 catalyst with the W/Si ratio of as low as 1/640 (Pt/W-SBA-15(1/640)) gave rise to the highest 1,3-PDO selectivity of 70.8% at a high glycerol conversion of 86.8% and thus afforded the highest yield of 1,3-PDO of 61.5%. A combination of characterization techniques evidenced that tungsten was homogeneously incorporated into SBA-15 in the form of isolated tetragonal WO₄ and only displayed Lewis acidity. The particle size of Pt evolved in a reverse volcanic curve with the W/Si ratio, with the smallest size being observed for Pt/W-SBA-15(1/640). Control experiments indicated strong synergy between Pt nanoparticles (NPs) and WO₄ in the hydrogenolysis of glycerol. A probe reaction suggested that Br?nsted acid sites were generated in situ on the Pt/W-SBA-15 catalysts in a H₂ atmosphere by the reaction between WO₄ and spillover H atoms from the Pt NPs. It is plausible that the hydrided WO₄ functioned as a highly selective active centre in the hydrogenolysis of glycerol to 1,3-PDO, whereas the Pt NPs played the role of a reservoir of spillover H atoms. Thus, a good match between the isolated WO₄ and the small Pt NPs was responsible for the superior catalytic performance of Pt/W-SBA-15(1/640).

Full text of DOI:10.1039/c7gc00317j

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Green Chemistry
ARTICLE
Nanoparticulate Pt on mesoporous SBA-15 doped with extremely
low amount of W as highly selective catalyst for glycerol
hydrogenolysis to 1,3-propanediol†
Received 00th January 20xx,
Accepted 00th January 20xx
Yiqiu Fan,a Shijie Cheng,a Hao Wang,a Danhong Ye,b Songhai Xie,a Yan Pei,a Huarong Hu,b Weiming
DOI: 10.1039/x0xx00000x
Hua,a Zhen Hua Li,a Minghua Qiao*a and Baoning Zong*c
www.rsc.org/
It has been documented that the W-modified Pt catalysts with relatively high tungsten contents are effective for the
catalytic transformation of biodiesel-derived glycerol to 1,3-propanediol (1,3-PDO). Herein, we report a new finding that
the Pt/W–SBA-15 catalysts with extremely low W/Si atomic ratios (1/80) exhibited excellent catalytic performances in
glycerol hydrogenolysis to 1,3-PDO. In particular, the Pt/W–SBA-15 catalyst with the W/Si ratio as low as 1/640 (Pt/W–
SBA-15(1/640)) gave rise to the highest 1,3-PDO selectivity of 70.8% at high glycerol conversion of 86.8%, thus rendering
the highest 1,3-PDO yield of 61.5%. A combination of the characterization techniques evidenced that tungsten was
homogeneously incorporated into SBA-15 in the form of isolated tetragonal WO4 and of only Lewis acidity. The particle
size of Pt evolved in a reversed volcanic curve with the W/Si ratio, with the smallest size being observed on Pt/W–SBA-
15(1/640). Control experiments pointed to a strong synergy between the Pt nanoparticles (NPs) and WO4 in glycerol
hydrogenolysis. Probe reaction suggested that Brønsted acid sites were generated in situ on the Pt/W–SBA-15 catalysts in
the H2 atmosphere by the reaction between WO4 and spillover H atoms from the Pt NPs. It is plausible that the hydrided
WO4 functions as the highly selective active centre in the hydrogenolysis of glycerol to 1,3-PDO, while the Pt NPs play the
role as the reservoir of spillover H atoms, thus a good matching between the isolated WO4 and the small-sized Pt NPs is
responsible for the superior catalytic performance of Pt/W–SBA-15(1/640).
amounts,3−6 which complies with the result of quantum
mechanical calculations that for glycerol the activation energy
for the cleavage of the terminal hydroxyl group is 9.6 kJ mol–1
lower than that of the secondary hydroxyl group.7 It is
apparent that the central challenge in transforming glycerol to
1,3-PDO is the design of catalysts capable of abstracting the
secondary hydroxyl group, while leaving the terminal hydroxyl
groups in glycerol as well as in 1,3-PDO unaffected.
Up to now, the Pt-sulfated ZrO2 catalyst,8 the Re-modified
noble metal catalysts,9−11 and the W-modified Pt catalysts12−16
are the most prevailing heterogeneous catalysts for glycerol
hydrogenolysis to 1,3-PDO. However, the Pt-sulfated ZrO2
catalyst is only selective in organic medium, which suffers from
huge energy consumption to evaporate water from crude
glycerol containing ca. 70% of water.17 The Re-modified noble
metal catalysts necessitate sulfuric acid as the additive in most
cases,9,10,18 which is plagued by corrosiveness to the reactor
and unfriendliness to the environment. In addition, Re is far
more expensive than W, and the high water solubility of ReOx
undermine the catalytic stability.2 Therefore, the W-modified
Pt catalysts are more promising for practical applications and
become the research focus in recent years.
Introduction
There has been a great surge in the production of biodiesel as
an alternative fuel via transesterification of vegetable oils and
animal fats to enable the shift of the energy supply from crude
oil to biomass. Since producing 100 kg of biodiesel generates
simultaneously about 10.5 kg of glycerol,1,2 it is of essential
importance to improve the value of the redundant glycerol. As
one of the higher-value products derived from glycerol, 1,3-
PDO serves as a monomer for polytriethylene terephthalate
(PTT) that has the softness of nylon, the fluffiness of acrylic
fibers, the stain resistance of polyethylene terephthalate (PET),
aside from its excellent elasticity and ability to be dyed at
room temperature. Unfortunately, the terminal hydroxyl
groups of glycerol are more inclined to leave, hence on most
catalysts the low-priced 1,2-PDO was produced in greater
aCollaborative Innovation Centre of Chemistry for Energy Materials, Department of
Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative
Materials, Fudan University, Shanghai 200433, P. R. China.
E-mail: mhqiao@fudan.edu.cn
bShanghai Institute of Space Power-Sources, Shanghai 200245, P. R. China.
cState Key Laboratory of Catalytic Materials and Chemical Engineering, Research
Institute of Petroleum Processing, SINOPEC, Beijing 100083, P. R. China.
E-mail: zongbn.ripp@sinopec.com
In a preliminary work, Kurosaka et al. reported that the
Pt/WO3/ZrO2 catalyst with 19.6 wt% of WO3 could afford the
1,3-PDO selectivity of 24.2% at glycerol conversion of 85.8% in
glycerol hydrogenolysis at 443 K using 1,3-dimethyl-2-
†Electronic
Supplementary
Information
(ESI)
available.
See
DOI: 10.1039/x0xx00000x
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Table 1 Basic physicochemical properties of the SBA-15, Pt/SBA-15, and Pt/W–SBA-15 samples
Pt loadinga
(wt%)
W/Sia
SBET
Vpore
dpore
d10
ac
(nm)
Dd
(%) (m2 gPt
SPt
Particle size (nm) Acid amounte
b
b
b
c
d
Sample



1
(atomic ratio) (m2 g ) (cm3 g ) (nm)
(nm)
10.6
10.6
10.6
10.7
10.7
10.8
10.8
10.8
)
(molNH3 gcat
)
1
1
–1
XRD
–
TEM
–
SBA-15
Pt/SBA-15
–
–
–
804
769
802
848
926
748
739
708
1.3
1.2
1.4
1.4
1.6
1.3
1.3
1.3
6.3
6.4
6.7
6.8
6.8
7.0
7.0
7.1
12.2
12.2
12.3
12.3
12.4
12.4
12.4
12.5
–
–
13
2.91
2.97
2.95
2.96
2.98
2.94
2.97
14.0
21.1
22.0
23.4
15.7
12.8
10.3
35
52
54
58
39
32
25
7.3
7.2
6.1
6.0
6.2
7.1
9.3
7.4
6.0
5.5
4.7
7.0
7.5
9.2
41
Pt/W–SBA-15(1/1280)
Pt/W–SBA-15(1/960)
Pt/W–SBA-15(1/640)
Pt/W–SBA-15(1/320)
Pt/W–SBA-15(1/160)
Pt/W–SBA-15(1/80)
1/1271
1/954
1/632
1/316
1/159
1/79
145
151
178
365
422
462
a Determined by ICP–AES. b Determined by N2 physisorption. c Derived from SAXS with d10 = 2π/q10 and a = d10/3. d Dispersion and active surface area of Pt determined
by CO chemisorption. e Determined by NH3-TPD.
imidazolidinone as the solvent.12 Subsequently, Chen and co- and Pt/WO3/AlOOH catalysts.13 This is the first work
workers reported the 1,3-PDO selectivity of 45.6% at glycerol demonstrating and elaborating that tungsten in such a trace
conversion of 70.2% at 403 K over the Pt/WO3/ZrO2 catalyst amount can impose a dramatic effect on the selectivity to 1,3-
with 10 wt% of W.19 Ding and co-workers found that on the PDO in glycerol hydrogenolysis over the W-modified Pt catalyst.
Pt/WO3/TiO2/SiO2 catalyst with 5 wt% of WO3, the 1,3-PDO
selectivity was 50.5% at glycerol conversion of 15.3%.4 Zhu et
al. prepared the Li-modified Pt–H4SiW12O40/ZrO2 catalysts with
Results and discussion
20 wt% of H4SiW12O40 and acquired the 1,3-PDO selectivity of
53.6% at glycerol conversion of 43.5%.20 On the SiO2-modified
Composition and texture
By inductively coupled plasma-atomic emission spectroscopy
(ICP–AES), we identified that the practical Pt loadings and W/Si
ratios on the Pt/SBA-15 and Pt/W–SBA-15 catalysts were close
to the nominal loadings (Table 1). Fig. S1† shows their N2
adsorption–desorption isotherms and the corresponding
Barrett–Joyner–Halenda (BJH) pore size distribution. The
catalysts displayed type IV isotherms with H1 hysteresis loops
and the most probable pore size of ca. 6.8 nm, signifying the
presence of ordered mesoporous structure. As compiled in
Table 1, the Brunauer–Emmett–Teller surface area (SBET) of
siliceous SBA-15 was 804 m2 g–1, which after the loading of Pt
decreased to 769 m2 g–1. For the Pt/W–SBA-15 catalysts, the
SBET increased with the W/Si ratio first, maximized on Pt/W–
SBA-15(1/640), and then decreased monotonically at higher
W/Si ratios. CO chemisorption revealed that Pt/W–SBA-
15(1/640) displayed the highest active surface area (SPt) and
dispersion (D) of Pt, which decreased upon increasing or
decreasing the W/Si ratio (Table 1).
Pt/WOx/ZrO2 catalyst with 15 wt% of WO3, the 1,3-PDO
selectivity was 52.0% at glycerol conversion of 54.3%.21 The
1,3-PDO selectivity was improved to 66.1% at glycerol
conversion of 64.2% on the Pt–WOx/Al2O3 catalyst with 10 wt%
of WO3.14 Kaneda and co-workers reported the record-high
1,3-PDO yield of 66–69% over the Pt/WO3/AlOOH catalyst with
8.0 wt% of W.13 Chary and co-workers developed a Pt–
WO3/SBA-15 catalyst with 10 wt% of WO3 being introduced by
post-modification of SBA-15, which afforded the 1,3-PDO
selectivity of 42% at glycerol conversion of 86%.15 Recently,
Zhang and co-workers reported that the mesoporous WOx-
supported single/pseudo-single atom Pt catalyst showed the
1,3-PDO yield of 21.7% and the highest space-time yield to 1,3-
–1
PDO of 3.78 g gPt h–1 among the W-modified Pt catalysts.16
Without exception, the tungsten contents ln all the optimized
W-modified Pt catalysts for glycerol hydrogenolysis to 1,3-PDO
fall in the range of medium to high surface densities of
tungsten according to the classification of Iglesia and co-
workers.22 It was generally suggested that the highest
Brønsted acidity at relatively high tungsten contents is
responsible for the highest selectivity to 1,3-PDO.2,4,14,20
Herein, we report about an unprecedented finding that at
extremely low contents of tungsten (W/Si = 0, 1/1280, 1/960,
1/640, 1/320, 1/160, and 1/80, atomic ratio), the Pt/W–SBA-15
catalysts synthesized by incorporating tungsten into SBA-15 via
the sol–gel strategy displayed excellent catalytic performances
in glycerol hydrogenolysis to 1,3-PDO; details for catalyst
preparation, characterization, and catalytic testing can be
found in the ESI†. The Pt/W–SBA-15 catalyst with the nominal
W/Si atomic ratio as low as 1/640, denoted as Pt/W–SBA-
15(1/640), performed comparably to the top catalysts
reported so far, including the Pt-sulfated ZrO2,8 Ir–ReOx/SiO2,9
Structure and morphology
The small-angle X-ray scattering (SAXS) patterns of the Pt/SBA-
15 and Pt/W–SBA-15 catalysts are presented in Fig. 1. Similar
to siliceous SBA-15, they displayed four well-resolved
scattering peaks indexible to the (10), (11), (20), and (21)
reflections of a two-dimensional hexagonal mesostructure
(space group p6mm).23 The (10) reflection shifted slightly to
lower q values with the increase in the W/Si ratio, indicating
the slight expansion of the interplanar spacing. The d10 and
unit cell parameter (a) of SBA-15 and W–SBA-15 in the
catalysts are summarized in Table 1, both of which increased
slightly but monotonically with the W/Si ratio from 0 to 1/80,
2 | J. Name., 2012, 00, 1-3
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a
b
c
d
e
f
Fig. 3 HAADF−STEM images of (a) the W−SBA-15(1/640) support and (b) the Pt/W−SBA-
15(1/640) catalyst.
g
211
a
0.05
0.10
0.15
0.20
q (nm1)
b
Fig. 1 SAXS patterns of the Pt/W–SBA-15 catalysts with the W/Si atomic ratios of (a) 0,
(b) 1/1280, (c) 1/960, (d) 1/640, (e) 1/320, (f) 1/160, and (g) 1/80.
c
d
e
 Pt
Amorphous silica



a
b
c
d
e
f
267
g
200
300
400
500
600
Wavelength (nm)
f
Fig. 4 UV–vis DRS spectra of the Pt/W–SBA-15 catalysts with the W/Si atomic ratios of
(a) 0, (b) 1/1280, (c) 1/960, (d) 1/640, (e) 1/320, (f) 1/160, and (g) 1/80.
g
20
30
40
50
60
70
80
2(degree)
bending), and 271 cm−1 (W–O–W deformation) (Fig. S2†).25
Fig. S3† displays the transmission electron microscopic (TEM)
images and particle size distribution (PSD) histograms of the
Pt/SBA-15 and Pt/W–SBA-15 catalysts. The mesoporous
structure of SBA-15 was well preserved with the doping of
tungsten and after the loading of platinum. Analogous to the
assignment on Pt/SBA-15, the dark particles on the Pt/W–SBA-
15 catalysts are assigned to the Pt NPs instead of the W-
containing species. This assignment is further supported by the
high-angle annular dark field scanning transmission electron
microscopic (HAADF–STEM) images in Fig. 3, which shows no
bright dots on the W–SBA-15(1/640) support, while the bright
dots are readily visible on Pt/W–SBA-15(1/640). As also
compiled in Table 1, with the increase in the W/Si ratio, the
size of the Pt NPs decreased first, minimized at 4.7 nm on
Pt/W–SBA-15(1/640), and then increased, which is parallel to
the evolution of the Pt crystallite size derived from XRD.
Fig. 2 Wide-angle XRD patterns of the Pt/W–SBA-15 catalysts with the W/Si atomic
ratios of (a) 0, (b) 1/1280, (c) 1/960, (d) 1/640, (e) 1/320, (f) 1/160, and (g) 1/80.
signifying the incorporation of tungsten cations (atomic radius
0.68 Å for W6+ vs. 0.40 Å for Si4+) into SBA-15.
Fig. 2 shows the wide-angle X-ray diffraction (XRD) patterns
of the Pt/SBA-15 and Pt/W–SBA-15 catalysts. Aside from the
broad feature at 2
are small peaks at 2

of ca. 22o from amorphous silica,24 there
of 39.8o, 46.1o, and 67.6o ascribable to

the (111), (200), and (220) reflections of the face-centred cubic
(fcc) Pt (JCPDS 04-0802), respectively. On the basis of the
Scherrer equation and the full width at the half maximum
(fwhm) of the (111) peak, the crystallite sizes of Pt were
estimated (Table 1). With the increase in the W/Si ratio, the Pt
crystallite size decreased gradually from Pt/SBA-15 to Pt/W–
SBA-15(1/640), and then increased steadily, which is in
agreement with the results of CO chemisorption. On the other
hand, there is no diffraction peak assignable to crystalline WO3
on the Pt/W–SBA-15 catalysts, which is attributed to the
extremely low content and high dispersion of tungsten. In line
with the XRD results, the Raman spectra of the Pt/W–SBA-15
catalysts as well as the Pt/SBA-15 catalyst were featureless. In
contrast, the crystalline monoclinic WO3 (m-WO3) standard
gave distinct Raman bands at 807 (W–O stretching), 714 (W–O
Identity of tungsten species
The ultraviolet–visible diffuse reflectance spectroscopic (UV–
vis
DRS)
and
Fourier-transform
infrared
(FTIR)
characterizations were carried out to provide insights into the
structural details of the tungsten species of extremely low
contents and high dispersion. While the UV–vis DRS spectrum
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1591
L
DOIL: 10.1039/C7GC00317J
(SiO) of SiOH
964
(SiOSi)sym
SBA-15
809
a
a
b
c
d
e
b
c
d
e
f
g
f
g
1650
1600
1550
1500
1450
1400
960
805
Wavenumber (cm1)
(SiO) of SiOW
(SiOW)sym
Fig. 6 Py-IR spectra acquired at 373 K on the Pt/W–SBA-15 catalysts with the W/Si
atomic ratios of (a) 0, (b) 1/1280, (c) 1/960, (d) 1/640, (e) 1/320, (f) 1/160, and (g) 1/80.
1000
900
800
700
Wavenumber (cm1)
Fig. 5 FTIR spectra of the Pt/W–SBA-15 catalysts with the W/Si atomic ratios of (a) 0, (b)
agreement with the poor acidity of siliceous SBA-15.35 The acid
amount increased monotonically with the increase in the W/Si
ratio, reflecting that the incorporation of tungsten into SBA-15
can generate extra acid sites.36
1/1280, (c) 1/960, (d) 1/640, (e) 1/320, (f) 1/160, and (g) 1/80.
Fig. 6 presents the pyridine-adsorption FTIR (Py-IR) spectra
of the Pt/SBA-15 and Pt/W–SBA-15 catalysts in order to unveil
the nature of the acid sites. For siliceous SBA-15, the bands at
1591 and 1445 cm–1 are readily ascribable to pyridine
coordinated to Lewis acid sites.37 As expected, only bands
characteristic of Lewis acid sites were present on Pt/SBA-15.
However, even on Pt/W–SBA-15(1/80) with the highest W/Si
ratio, tungsten did not invoke Brønsted acid sites that should
give band at about 1540 cm–1 associated with the W–(OH)–W
or W–OH groups.38,39 Rather, the amount of Lewis acid sites
increased continuously with the W/Si ratio, which can be
related to the occurrence of the W=O terminal groups.38
of Pt/SBA-15 is featureless, two bands centred at 211 and 267
nm emerged for the Pt/W–SBA-15 catalysts (Fig. 4). The
former is attributed to the isolated tungsten species in a
tetrahedral coordination environment (WO4),26,27 whereas the
latter can be associated with the tungsten species in a
distorted tetrahedral or an octahedral coordination
environment,28 which will be further discriminated below.
Fig. 5 shows the FTIR spectra of the Pt/SBA-15 and Pt/W–
SBA-15 catalysts. For Pt/SBA-15, the bands at 964 and 809 cm–
1
are assigned to the Si–O stretching vibration in Si–O–H and
the symmetric stretching vibration of Si–O–Si in tetrahedral
SiO4,29,30 respectively. For the Pt/W–SBA-15 catalysts, with the
increase in the W/Si ratio, the maxima of both bands shifted to
lower wavenumbers and stabilized at 960 and 805 cm–1. The
former is an indication of the incorporation of metal ions into
silica with the Si–O stretching vibration being perturbed by
neighbouring metal ions.31,32 The latter is ascribed to the
symmetric stretching vibration of Si–O–W.29 Considering that
there is no band at about 875 cm–1 characteristic of the W–O
stretching vibration of the octahedral WO6 unit,33 the UV-vis
DRS band at 267 nm in Fig. 4 is then attributed to the tungsten
species in a distorted tetrahedral coordination environment.
Furthermore, the band characteristic of the asymmetric
stretching vibration of W–O–W at about 890 cm–1 is also
lacking,34 manifesting that the tungsten species are
monomeric rather than polymeric. Therefore, the tungsten
species on the Pt/W–SBA-15 catalysts with extremely low
contents of tungsten can be unambiguously represented as
the isolated tetrahedral WO4.
Interaction between Pt and WO4
Fig. 7 displays the Pt 4f spectra of the Pt/SBA-15 and Pt/W–
SBA-15 catalysts; the fitting results are summarized in Table 2.
The spectra can be fitted into two groups of doublets with the
Pt 4f7/2 BEs of ca. 71.1 and 72.8 eV ascribable to Pt0 and Pt2+,
respectively.40 As listed in Table 2, the surface Pt2+/(Pt0 + Pt2+)
ratio improved from Pt/SBA-15 to Pt/W–SBA-15(1/640), and
then descended gradually at higher W/Si ratios. Arribas et al.
observed Pt2+ on the Pt/WO3–ZrO2 catalyst and interpreted
this species as a sign of the strong interaction between the
highly dispersed Pt NPs and surface tungsten species.41 It is
plausible that the Pt2+ species are originated from the Pt atoms
at the periphery of the Pt NPs that bind to the support by
forming the Pt–O–Si/W linkages, which is a well-accepted
binding model for metal NPs on oxides.42,43 Because the Pt NPs
on Pt/W–SBA-15(1/640) are the smallest, this catalyst is
anticipated to have the largest number of the peripheral Pt–
O–Si/W linkages and hence the highest surface Pt2+/(Pt0 + Pt2+)
ratio. This result in turn infers the highest inclination of the W–
SBA-15(1/640) support to form the Pt–O–Si/W linkages with
the Pt NPs. Consistently, Table 2 also shows that Pt/W–SBA-
15(1/640) displayed the highest surface Pt/Si ratio. The XPS
results, along with the results of CO chemisorption and TEM,
point out that there is an optimal W/Si ratio, namely, 1/640, to
Acidic properties
The profiles of the temperature-programmed desorption of
NH3 (NH3-TPD) of the Pt/SBA-15 and Pt/W–SBA-15 catalysts
are displayed in Fig. S4†. The total acid amounts (nNH3
)
determined by integrating the areas under the desorption
peaks are also summarized in Table 1. Pt/SBA-15 exhibited a
weak desorption feature with low acid amount, which is in
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50
40
30
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a
b
PtPt
Pt foil
a
Pt2+
Pt0
PtO
c
b
c
20

d
e
10
d
0
0
2
4
6
8
f
R (Å)
Fig. 8 The RDFs after Fourier transformation of the Pt L2-edge k3-weighted (k) data of
the Pt/W–SBA-15 catalysts with the W/Si atomic ratios of (a) 0, (b) 1/1280, (c) 1/640,
and (d) 1/160. The RDF of the Pt foil is included as a reference.
g
82 80 78 76 74 72 70 68 66
Binding energy (eV)
Table 3 Structural parameters derived from the Pt L2-edge EXAFS data of the Pt foil and
the Pt/SBA-15 and Pt/W–SBA-15 catalysts
Fig. 7 Pt 4f spectra of the Pt/W–SBA-15 catalysts with the W/Si atomic ratios of (a) 0, (b)
1/1280, (c) 1/960, (d) 1/640, (e) 1/320, (f) 1/160, and (g) 1/80.
Sample
Pair
CNa Rb (Å) 2 (10–3 Å2) E0 (eV)
Table 2 XPS fitting results of the Pt/SBA-15 and Pt/W–SBA-15 catalysts
Pt foil
Pt/SBA-15
Pt–Pt
Pt–Pt
Pt–O
12.0
7.4
0.3
7.4
0.9
6.0
1.1
10.0
0.4
2.78
2.79
2.05
2.76
2.00
2.76
2.02
2.77
2.01
5.6
6.1
8.7
6.6
6.7
7.2
1.0
6.2
8.1
9.3
14.0
9.3
Pt 4f7/2 BE (eV)
Catalyst
Pt2+/(Pt0 + Pt2+)a
Pt/Sia
Pt0
Pt2+
72.8
72.8
72.8
72.9
72.8
72.8
72.8
Pt/W–SBA-15(1/1280) Pt–Pt
Pt–O
Pt/W–SBA-15(1/640)
6.8
9.9
Pt/SBA-15
71.1
71.1
71.2
71.2
71.1
71.1
71.2
0.06
0.08
0.09
0.10
0.08
0.08
0.07
0.51
0.85
0.85
0.95
0.80
0.72
0.64
Pt–Pt
Pt–O
Pt–Pt
Pt–O
6.1
Pt/W–SBA-15(1/1280)
Pt/W–SBA-15(1/960)
Pt/W–SBA-15(1/640)
Pt/W–SBA-15(1/320)
Pt/W–SBA-15(1/160)
Pt/W–SBA-15(1/80)
10.4
11.2
9.7
Pt/W–SBA-15(1/160)
a Error range: 10%. b Error range: 0.2 Å.
first, minimized at 4.8 for Pt/W–SBA-15(1/640), and then
increased at higher W/Si ratios. The smallest Pt–Pt CN of
Pt/W–SBA-15(1/640) is consistent with its smallest Pt NPs.
Different from the Pt foil, the Pt/SBA-15 and Pt/W–SBA-15
catalysts had an additional Pt–O coordination shell at ca. 2.03
Å,42 which is also present when fitting the k1- and k2-weighted
χ(k) data. The CN of the Pt–O shell evolved in an inversed trend
with respective to that of the Pt–Pt shell, maximizing at 1.1 on
Pt/W–SBA-15(1/640). Coupling with its highest surface
Pt2+/(Pt0 + Pt2+) ratio, the largest Pt–O CN of Pt/W–SBA-
15(1/640) corroborates the assumption that the Pt2+ species
are associated with the Pt–O–Si/W linkages that aid in
anchoring and dispersing small Pt NPs.
a Atomic ratio.
attain the strongest interaction between Pt and W–SBA-15. On
the other hand, because of the extremely low contents of
tungsten, the W 4f signals were not discernible even on Pt/W–
SBA-15(1/80).
Fig. 8 shows the non-phase corrected radial distribution
functions (RDFs) transformed from the Pt L2-edge k3χ(k) data
of Pt/SBA-15 and the representative Pt/W–SBA-15(1/1280),
Pt/W–SBA-15(1/640), and Pt/W–SBA-15(1/160) catalysts,
using Pt foil as the reference. Table 3 summarizes the
structural parameters extracted from the extended X-ray
absorption fine structure (EXAFS) data. The reliability of the
fittings is validated by the close resemblance of the simulated
curves to the experimental data (Fig. S5†). In Fig. 8, the
positions of the main peak of the Pt/SBA-15 and Pt/W–SBA-15
catalysts are identical to that of the first nearest Pt–Pt
coordination peak of the Pt foil. However, the much weaker
peak amplitudes of the catalysts indicate their much lower Pt–
Pt coordination numbers (CNs) as well as much smaller particle
sizes.44−46 Moreover, Table 3 shows that the Pt–Pt CN is
sensitive to the W/Si ratio. The CN of the Pt–Pt shell decreased
Hydrogenolysis of glycerol
The catalytic results of glycerol hydrogenolysis over the
Pt/SBA-15 and Pt/W–SBA-15 catalysts at 423 K and 4.0 MPa of
H2 are summarized in Table 4. On Pt/SBA-15, the conversion of
glycerol to liquid products (CTL) was only 3.4% after 30 h of
reaction, and the primary product was 1-propanol (1-PrOH),
followed by 2-PrOH and 1,2-PDO. The selectivity to the target
product, 1,3-PDO, was only 8.9%. Upon doping of siliceous
SBA-15 with a trace amount of tungsten (W/Si = 1/1280), it is
remarkable that the CTL and 1,3-PDO selectivity were boosted
respectively by one order of magnitude to 34.5% and more
than five folds to 47.5% under the same reaction conditions.
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Table 4. The catalytic results of glycerol hydrogenolysis over the Pt/SBA-15 and Pt/W–SBA-15 catalystsa
b
Sel. (C% in liquid products)
Conversion
(%)
CTL
(%)
Yield1,3-PDO
(%)
S0
TOF
c
Catalyst
r0
(%)
(h–1)
1,3-PDO 1,2-PDO
1-PrOH
63.8
2-PrOH
Others
3.8
Pt/SBA-15
4.0
3.4
8.9
10.6
1.8
12.9
7.5
0.31
16.4
34.5
15.8
52.3
73.4
0.1
1.1
1.4
2.8
Pt/W–SBA-15(1/1280)
Pt/W–SBA-15(1/960)
35.6
51.7
34.5
50.6
47.5
68.3
34.1
9.1
20.3
25.6
1.3
22.6
6.8
1.0
Pt/W–SBA-15(1/640)
Pt/W–SBA-15(1/320)
88.0
81.9
86.8
80.1
70.8
64.6
1.2
0.8
19.8
27.9
6.6
6.7
1.6
61.5
51.8
80.8
69.3
4.5
4.2
73.6
trace
107.3
Pt/W–SBA-15(1/160)
Pt/W–SBA-15(1/80)
70.1
50.1
69.4
49.5
52.3
48.4
0.9
2.1
37.4
42.0
5.3
5.2
4.1
2.3
36.3
24.0
60.2
58.6
1.7
0.9
51.4
34.0
a Reaction conditions: 200 mg of catalyst, 2.0 g of 30 wt% glycerol aqueous solution, temperature of 423 K, H2 pressure of 4.0 MPa, stirring rate of 500 rpm, and 30 h. b
Initial selectivity to 1,3-PDO. c Weight-specific activity, unit in mmol gcat–1 min–1. S0, r0, and TOF were acquired at CTL of 4.7–8.8%.
The CTL and 1,3-PDO selectivity increased steadily with the only 0.4–2.9% under the same reaction conditions (Table S2†).
W/Si ratio, reached the respective maxima of 86.8% and 70.8%
Tables S3† and S4† present the influences of the reaction
on Pt/W–SBA-15(1/640), thus giving the highest 1,3-PDO yield temperature and pressure on the catalytic performance of
of 61.5%. Then, the CTL and 1,3-PDO selectivity decreased Pt/W–SBA-15(1/640), respectively. As expected, with the
gradually at higher W/Si ratios. The 1,2-PDO selectivity, on the increase of the reaction temperature from 403 K to 443 K, the
other hand, was suppressed to no more than 2.1% on all the CTL increased, while the 1,3-PDO selectivity decreased. With
Pt/W–SBA-15 catalysts, showing that tungsten favourably the increase of the reaction pressure from 1.0 MPa to 4.0 MPa,
promotes the abstraction of the secondary hydroxyl group both the CTL and 1,3-PDO selectivity increased. Even higher
instead of the terminal hydroxyl group of glycerol. On Pt/W– pressure was not attempted for safety concerns. As a result, as
SBA-15(1/640), the initial selectivity to 1,3-PDO (S0) and the far as the 1,3-PDO yield is concerned, the optimum reaction
initial weight-specific reaction rate of glycerol (r0) were 80.8% temperature and pressure for Pt/W–SBA-15(1/640) were 423 K
–1
and 4.5 mmol gcat min–1, respectively, which are also the and 4.0 MPa, respectively.
highest among these catalysts. It is worth noting that the 1,3-
As an important character of a catalyst, the reusability of
PDO yield acquired on Pt/W–SBA-15(1/640) is among the top Pt/W–SBA-15(1/640) exhibiting the best catalytic performance
results reported so far (Table S1†), which is only inferior to the was examined. Fig. 9 shows that the CTL decreased
1,3-PDO yield of 66–69% on Pt/WO3/AlOOH with 8.0 wt% of W insignificantly from the 1st run to the 4th run. The ~2.7% per
at 453 K and 5 MPa of H2.13
run CTL drop is more likely caused by material loss due to
Apparently, for the Pt/SBA-15 and Pt/W–SBA-15 catalysts catalyst attrition in stirred liquid-phase reaction and repetitive
the one with larger SPt/smaller dPt gave rise to higher CTL in catalyst recovery than by the irreversible degradation of the
glycerol hydrogenolysis. Since Pt/W–SBA-15(1/640) had the catalyst, which is supported by the essentially invariant
largest SPt and the smallest dPt, it exhibited the highest CTL. product distribution including the selectivity to 1,3-PDO also
However, the CTLs were not directly proportional to SPt or depicted in Fig. 9. In addition, platinum and tungsten were not
inversely proportional to dPt. When we expressed the activity detected by ICP–AES in the supernatant after recycling, which
in terms of the turnover frequency (TOF) of glycerol on the excludes the leaching of the active components.
basis of r0 and SPt, it turns out that the TOFs were closely
Control experiments
dependent on the W/Si ratio. In the presence of tungsten, the
TOFs were about one order of magnitude of that on Pt/SBA-15 When the W–SBA-15(1/640) support alone was used as the
(Table 4), inferring the occurrence of strong synergy between catalyst in glycerol hydrogenolysis under otherwise the same
the Pt NPs and the isolated WO4. It should be noted that the reaction conditions, it gave low CTL of 2.6% and poor 1,3-PDO
discrepancy in the catalytic performance in the absence and selectivity of 6.5% (Table S2†). Interestingly, physically mixing
presence of tungsten is not due to the discrepancy in the Pt/SBA-15 with W–SBA-15(1/640) (Pt/SBA-15 + W–SBA-
particle size of Pt. For Pt/SBA-15 and Pt/W–SBA-15(1/160) 15(1/640)) to attain the same amounts of platinum and
with similar Pt sizes of 7.4 and 7.5 nm, respectively, they tungsten as those in Pt/W–SBA-15(1/640) dramatically
exhibited sharply different activities and selectivities (Table 4). improved the CTL to 84.9% (Table S2†), which even
Tungsten in extremely low amount is very unique in approaches the CTL on Pt/W–SBA-15(1/640). However, the
enhancing the activity and selectivity to 1,3-PDO. When 1,3-PDO selectivity on the physically mixed catalyst was 36.8%,
tungsten in Pt/W–SBA-15(1/640) was displaced by the same which is only about one-half of that on Pt/W–SBA-15(1/640)
amount of chromium or molybdenum in the same VIB group, and still lower than those on the Pt/W–SBA-15 catalysts with
or aluminium and vanadium that were frequently adopted to other W/Si ratios. These results further substantiate the strong
modify SBA-15 in a variety of catalytic applications,47−51 the synergy between the Pt NPs and the isolated WO4 on the
CTLs were only 0.8–7.6%, and the 1,3-PDO selectivities were Pt/W–SBA-15 catalysts, and to a lesser extent, even on the
6 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C7GC00317J
100
80
60
40
20
0
CTL
1,2-PDO
1,3-PDO
1-PrOH
2-PrOH
1
2
3
4
Run Number
Fig. 9 The CTL and product distribution in glycerol hydrogenolysis over the Pt/W–
SBA-15(1/640) catalyst in four successive runs. Reaction conditions: 200 mg of
catalyst, 2.0 g of 30 wt% glycerol aqueous solution, temperature of 423 K, H2 pressure
of 4.0 MPa, stirring rate of 500 rpm, and 30 h.
100
Scheme 1 Proposed reaction mechanism for glycerol hydrogenolysis to 1,3-PDO over
the Pt/W–SBA15 catalysts.
Pt/WSBA-15
Pt/SBA-15
80
60
40
20
0
92.9 manifests that Pt/W–SBA-15(1/640) is more effective in
abstracting the secondary hydroxyl group than the primary
hydroxyl group. For comparison, the hydrogenolysis of 1,2-
PDO on Pt/SBA-15 resulted in 1-PrOH selectivity of 66.0% and
2-PrOH selectivity of 5.8%. The corresponding 1-PrOH to 2-
PrOH ratio was only 11.4. These results unambiguously verify
that the presence of the isolated WO4 preferentially promotes
the hydrogenolysis of the secondary hydroxyl group in polyols,
thus improving the selectivity to 1,3-PDO in glycerol
hydrogenolysis.
Glycerol
1,3-PDO
1,2-PDO
Fig. 10 Hydrogenolysis performance of glycerol, 1,2-PDO, and 1,3-PDO over the Pt/W–
SBA-15(1/640) catalyst. Reaction conditions: 200 mg of catalyst, 2.0 g of 30 wt%
aqueous solution of the substrate, temperature of 423 K, H2 pressure of 4.0 MPa,
stirring rate of 500 rpm, and 30 h.
Interpretation of the synergy between Pt and W
For the Pt/W–SBA-15 catalysts with the W–SBA-15 supports
being synthesized by the sol–gel strategy containing far less
amounts of tungsten than those in previous W-modified Pt
catalysts for glycerol hydrogenolysis to 1,3-PDO,4,12−16,19−21 XRD
and Raman indicated that tungsten was highly dispersed
without forming crystalline WO3. UV–vis DRS and FTIR verified
that the tungsten species were individually incorporated into
SBA-15 through the Si–O–W bonding with tungsten in the
tetragonal coordination environment (WO4). Py-IR revealed
that the Pt/W–SBA-15 catalysts contained solely Lewis acid
sites. According to Galano et al.,52 there are two types of
monomeric WO4, bidentate [(–O–)2W(=O)2] and unidentate [(–
O–)W(=O)2(–OH)]. The former only shows Lewis acidity, while
the latter shows both Lewis and Brønsted acidity. Therefore,
the isolated WO4 on the Pt/W–SBA-15 catalysts may be more
properly depicted as bidentate [(Si–O–)2W(=O)2].
The high 1,3-PDO selectivities on the Pt/W–SBA-15 catalysts
in glycerol hydrogenolysis with only Lewis acidity seems in
contradiction with the overwhelming experience that Brønsted
acid sites favour the formation of 1,3-PDO, while Lewis acid
sites favour the formation of 1,2-PDO.4,8,12,20,53,54 In light of
above experimental facts and the reaction mechanisms
proposed previously,2,9,13,55 we put forward the following
physically mixed Pt/SBA-15 + W–SBA-15(1/640) catalyst.
Moreover, it turns out that the presence of the Pt NPs and
WO4 on the same catalyst grain is not a necessary prerequisite
to a high catalytic activity in glycerol hydrogenolysis, but it is of
prime importance to achieve a high 1,3-PDO selectivity.
Further, when we substituted 1,3-PDO for glycerol under
otherwise the same reaction conditions on Pt/W–SBA-
15(1/640), the CTL of 1,3-PDO was 9.7% (Fig. 10), which is
much lower than that of glycerol, showing that the
hydrogenolysis of 1,3-PDO is effectively blocked on this
catalyst. The poor capability of Pt/W–SBA-15(1/640) to
catalyse the hydrogenolysis of 1,3-PDO is advantageous to a
high 1,3-PDO selectivity in glycerol hydrogenolysis.
In contrast, when 1,2-PDO was employed as the reactant
under otherwise the same reaction conditions on Pt/W–SBA-
15(1/640), the CTL of 1,2-PDO amounted to 91.2% (Fig. 10),
which is even higher than that of glycerol. This result infers
that Pt/W–SBA-15(1/640) is highly capable of catalysing the
hydrogenolysis of polyols with both the primary and secondary
hydroxyl groups. Moreover, 1-PrOH was the predominant
product with high selectivity of 92.9%, while the 2-PrOH
selectivity was only 1.0%. The high 1-PrOH to 2-PrOH ratio of
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mechanism to account for the unusual catalytic behaviours of produces 3-hydroxypropoxide (Step 4, Scheme 1). Finally, the
View Article Online
the Pt/W–SBA-15 catalysts with extremely low tungsten hydrolysis of 3-hydroxypropoxide relDeOasI:e1s0.1013,93/-CP7DGOC003a1n7dJ
contents, as illustrated in Scheme 1. With the coexistence of restores the active centre (Step 5, Scheme 1), thus completing
the Pt NPs and the isolated WO4, H atoms dissociated from H2 the catalytic cycle.
molecules on the Pt NPs spillover onto WO4. The hydrided
According to Scheme 1, considering that the six-membered
WO4, most likely with one W=O group being changed to H–W– ring formed between secondary hydroxyl group and tungsten
OH (Step 1, Scheme 1), plays the role as the active centre for is more stable than the seven-membered ring formed between
glycerol hydrogenolysis. This assumption is supported by the terminal hydroxyl group and tungsten, the substrate with the
facts that while the activity of Pt/SBA-15 and W–SBA-15(1/640) hydroxyl groups at both the primary and secondary positions
alone was poor, when they were mixed together, the activity (glycerol and 1,2-PDO) should be more reactive than 1,3-PDO
became comparable to that of Pt/W–SBA-15(1/640). The with only terminal hydroxyl groups, which is validated by the
formation of the hydrided WO4 represents a physical catalytic results illustrated in Fig. 10. Also, the preferential
description of the synergy between the Pt NPs and the isolated formation of 1,3-PDO and 1-PrOH respectively from glycerol
WO4, and is consistent with the “molecular hydrogen- and 1,2-PDO on Pt/W–SBA-15(1/640) (Table 4 and Fig. 10) can
originated protonic acid site” model proposed on the Pt/WO3– be satisfactorily explained by this mechanism. In addition,
ZrO2 catalyst in the presence of H2.56
García-Fernández et al. suggested that the fast hydrogenation
To validate the in situ generation of the protonic acid site, of the secondary carbocation is a key step to avoid its further
i.e., Brønsted acid site, on the Pt/W–SBA-15 catalysts by conversion into acrolein, a precursor to 1-PrOH.2 Because the
spillover H atoms during glycerol hydrogenolysis, we co-fed H2 surface diffusion of H atoms is usually regarded as a slow
with Py when conducting the Py-IR experiment and collected step,56 it is conceivable that the diffusion distance for H atoms
the spectra also in the H2 atmosphere at 373 K. However, we from the Pt NPs to the W-containing carbocation on the Pt/W–
did not observe the characteristic band of Py on Brønsted acid SBA-15 catalysts with the Pt NPs and WO4 on the same catalyst
site at ~1540 cm–1 (Fig. S6†), possibly due to the low grain is shorter than that on the physically mixed Pt/SBA-15 +
concentration of Brønsted acid sites at ambient H2 pressure W–SBA-15(1/640). Therefore, the hydrogenation of the
and/or the high reversibility of H atoms migrating between the secondary carbocation is faster and the 1,3-PDO selectivities
Pt NPs and tungsten oxide.57 Hence, cumene cracking, a are higher while the 1-PrOH selectivities are lower on the
sensitive probe reaction catalysed specifically by Brønsted acid Pt/W–SBA-15 catalysts than on the physically mixed catalyst
sites,58 was adopted to examine the Brønsted acidity of Pt/W– (Table S2†). Since H2 dissociation is necessary before becoming
SBA-15(1/640). Fig. S7† shows that the conversion of cumene H atoms, and the Pt NPs on the Pt/W–SBA-15 catalysts
using H2 as the carrier gas was eight folds of that using He as dissociate and store H atoms required for hydrogen spillover, it
the carrier gas under otherwise the same reaction conditions, is anticipated that Pt/W–SBA-15(1/640) with the smallest Pt
which unequivocally confirms that Pt/W–SBA-15(1/640) NPs is the most effective in providing spillover hydrogen to
generates Brønsted acid sites in situ in the presence of H2.40 On WO4 considering its largest SPt available for the dissociation of
the other hand, the possibility of the generation of the H2 (Table 1), thus affording the highest activity and selectivity
Brønsted acidity by hydrolysing the isolated WO4 with water to 1,3-PDO among the Pt/W–SBA-15 catalysts.
during the reaction should be minimal, if any, as this would
cause the leaching of tungsten and notably deteriorate the
catalytic stability, which is not compatible with the good
Conclusions
reusability demonstrated above.
We report for the first time the excellent catalytic
performance and the plausible working mechanism of the
Pt/W–SBA-15 catalysts with extremely low tungsten contents
in the selective production of 1,3-PDO from glycerol. The
tungsten species on the Pt/W–SBA-15 catalysts was identified
as the isolated WO4 with Lewis acidity. During the reaction, the
synergy between the Pt NPs and WO4 in the H2 atmosphere led
to the in situ generation of the hydrided WO4 by spillover H
atoms from the former to the latter, which functions as the
highly selective centre for glycerol hydrogenolysis to 1,3-PDO.
The good matching between the dimension of the Pt NPs and
the isolated WO4 is essential to a high 1,3-PDO selectivity. This
work affords a new strategy for the design of a high-
performance catalyst by deploying extremely low amount of
tungsten as the co-catalyst to selectively transforming glycerol
to 1,3-PDO.
After the creation of the active centre, its W–OH group
acting as Brønsted acid site catalyses the dehydration of the
terminal hydroxyl group of glycerol to form 2,3-
dihydroxypropoxide (Step 2, Scheme 1) with minimal steric
repulsion,59 an adsorption configuration also proposed on the
Pt/WOx/Al2O3,2 Ir–ReOx/SiO2,9 Pt–AlOx/WO3,55 and Rh–
ReOx/SiO2 catalysts.60 Subsequently, the secondary hydroxyl
group of 2,3-dihydroxypropoxide attacks the nearby W–H
bond via a six-membered ring structure. After dehydration, an
adsorbed secondary carbocation is formed (Step 3, Scheme
1).2,55 Then, two H atoms diffused from the Pt NPs combine
with the negatively charged W and the secondary carbocation
in a way analogous to the “molecular hydrogen-originated
protonic acid site” model.56 Namely, one H atom undergoes
surface diffusion to secondary carbocation where it releases
an electron to the carbocation and becomes a proton, which is
stabilized on the negatively charged W. The other H atom
combines with the electron trapped at the carbocation and
Acknowledgements
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C, 2013, 117, 26385–26395.
This work was supported by the State Key Research and
Development Project of China (2016YFB0301602,
2012CB224804), the National Natural Science Foundation of
China (21373055), the Science and Technology Commission of
Shanghai Municipality (08DZ2270500), and the Beijing
Synchrotron Radiation Facility (BSRF).
View Article Online
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DOI: 10.1039/C7GC00317J
Graphical contents entry
Nanoparticulate Pt on mesoporous SBA-15 doped with extremely low amount of W as highly
selective catalyst for glycerol hydrogenolysis to 1,3-propanediol
Yiqiu Fan, Shijie Cheng, Hao Wang, Danhong Ye, Songhai Xie, Yan Pei, Huarong Hu, Weiming
Hua, Zhen Hua Li, Minghua Qiao,* and Baoning Zong*
Pt/W–SBA-15 catalyst with extremely low W/Si atomic ratio of 1/640 affords high 1,3-PDO selectivity
and yield in glycerol hydrogenolysis.