Topics in Catalysis (2023) 66:205–222

https://doi.org/10.1007/s11244-022-01753-9

ORIGINAL PAPER

Structure‑Activity Relationships of Pt‑WOx/Al2O3 Prepared

with Different W Contents and Pretreatment Conditions for Glycerol
Conversion to 1,3‑Propanediol
Napaphut Dolsiririttigul1,2 · Thanapha Numpilai3 · Chularat Wattanakit4 · Anusorn Seubsai1,2 ·
Kajornsak Faungnawakij5 · Chin Kui Cheng6 · Dai‑Viet N. Vo7 · Supinya Nijpanich8 · Narong Chanlek8 ·
Thongthai Witoon1,2 

Accepted: 17 November 2022 / Published online: 30 November 2022

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2022

Abstract
Turning waste glycerol into a fundamental chemical used in the petrochemical industry offers an opportunity to reduce not
only waste from biodiesel production but also the consumption of petroleum-based chemicals. In the present work, glyc-
erol was converted to 1,3-propanediol over Pt-WOx/Al2O3 catalysts, while focusing on the influence of W loading contents
(10–20 wt.%) and catalyst pretreatment conditions, specifically the calcination temperatures of ­WOx/Al2O3 (700–900 °C),
calcination temperatures of Pt-WOx/Al2O3 (350–450 °C) and reduction temperatures of Pt-WOx/Al2O3 (300–400 °C). The
characteristics of the catalysts were identified by applying ­N2-sorption, XRD, Raman, CO pulse chemisorption, ­NH3-TPD,
­H2-TPR, ­H2-TPD, SEM and TEM-EDS and XPS. The W loading contents and pretreatment conditions strongly affected
the activity and products selectivity. The W content and calcination temperature of W ­ Ox/Al2O3 at 15 wt.% and 800 °C,
respectively, were evaluated as the most suitable in providing optimum W-O-W clusters to generate ­Hδ+ which was a key
parameter for the generation of 1,3-propanediol. The calcination and reduction temperatures of Pt-WO x/Al2O3 at 400 °C
and 350 °C, respectively, were mandatory to sufficiently convert P ­ tCl2 to P
­ t3O4 and P
­ t3O4 to metallic Pt, respectively. The
optimized Pt-WOx/Al2O3 catalyst achieved a high glycerol conversion (44.7%) with high selectivity toward 1,3-propanediol
(45.1%) under a reaction temperature and pressure of 220 °C and 60 bar, respectively.

Keywords  Glycerol conversion · 1,3-Propanediol · W loading · Pretreatment conditions · Pt-WOx/Al2O3 catalyst

4
* Thanapha Numpilai Department of Chemical and Biomolecular Engineering,
thanapha@tu.ac.th Vidyasirimedhi Institute of Science and Technology,
Rayong 21210, Thailand
* Thongthai Witoon
5
fengttwi@ku.ac.th National Nanotechnology Center (NANOTEC), National
Science and Technology Development Agency (NSTDA),
1
Department of Chemical Engineering, Faculty Pathum Thani 12120, Thailand
of Engineering, Center of Excellence on Petrochemical 6
Department of Chemical Engineering, Center for Catalysis
and Materials Technology, Kasetsart University,
and Separation (CeCaS), College of Engineering, Khalifa
Bangkok 10900, Thailand
University, Abu Dhabi, United Arab Emirates
2
Center for Advanced Studies in Nanotechnology 7
Centre of Excellence for Green Energy and Environmental
for Chemical, Food and Agricultural Industries, Kasetsart
Nanomaterials (CE@GrEEN), Nguyen Tat Thanh University,
University, Bangkok 10900, Thailand
Ho Chi Minh City 755414, Vietnam
3
Department of Environmental Science, Faculty 8
Synchrotron Light Research Institute,
of Science and Technology, Thammasat University,
Nakhon Ratchasima 30000, Thailand
Pathum Thani 12120, Thailand

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1 Introduction
1,3-Propanediol is a building block of polytrimethylene
terephthalate (PTT) applied in fibers for the manufactur-
ing of textiles, carpets and advanced thermoplastics [1].
1,3-Propanediol is produced industrially by two different
routes, consisting of acrolein hydration [2] and ethylene
oxide hydroformylation [2], using fossil resources as the
raw material. Due to the dwindling fossil resources and
negative environmental impacts of their usage, it is nec-
essary to find an alternative more sustainable raw mate-
rial with reduced environmental impacts [3–8]. Instead of
fossil resources, bio-based raw materials are considered
as a carbon-neutral resource for the sustainable produc-
tion of chemicals. The commercially available process
for the transformation of bio-based raw material to fuel is
the production of biodiesel derived from the reaction of
triglycerides with a small molecule of alcohol [9, 10]. In
addition to biodiesel, glycerol is inevitably produced as a
by-product which accounts for approximately 10 wt.% of
the total product [11–13]. Therefore, the utilization of the
by-product (glycerol) as the raw material for the synthesis
of 1,3-propanediol offers advantages of being economi-
cally feasible and environmentally benign.
Glycerol can be dehydrated and hydrogenated over
bifunctional catalysts containing acid and metal func-
tions, respectively, to form various kinds of products,
such as 1,3-propanediol, 1,2-propanediol and propanol [2].
1,3-Propanediol is favorable from an economic viability
point of view to efficiently consume H ­ 2. Two groups of
supported catalysts (Pt-WOx-supported catalysts [14–16]
and Ir-ReO x -supported catalysts [17, 18]) have been
found to be selective for the formation of 1,3-propanediol.
García-Fernández et al. [19] pointed out that Brønsted acid
sites and close contact of Pt and ­WOx were crucial factors
for the selective conversion of glycerol to 1,3-propanediol.
Zhu et al. [20] varied W loading contents (5, 10, 15 and
20 wt.% of Pt-WOx/Al 2O 3 catalysts) while the calcina-
tion temperatures of W ­ Ox/Al2O3 and Pt-WOx/Al2O3 were
defined at 600 °C and 400 °C, respectively. The maximum
1,3-propanediol yield of 42.4% was gained over Pt-WOx/
Al2O3 with 10 wt.% W loading. Lei et al. [21] varied the
composition of Pt and W ­ O x in the range 1–8 wt.% and
1–40 wt.%, respectively. All the ­WOx/Al2O3 and Pt-WOx/
Al2O3 were calcined at 700 °C and 300 °C, respectively.
The highest 1,3-propanediol yield was attained over Pt-
WOx/Al2O3 with 6 wt.% Pt and 12.9 wt.% W loading con-
tents. Kitano et al. [22] studied the effect of the calcination
temperature of W ­ Ox/Al2O3 from 500 to 1150 °C and W
loading ranging from 5 to 50 wt.% on the formation of
Brønsted acid sites. They found that the Brønsted acid
sites were maximized when the calcination temperature of
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Topics in Catalysis (2023) 66:205–222
­WOx/Al2O3 and the W loading were 20 wt.% and 900 °C,
respectively. Unfortunately, the catalytic performance
of those catalysts for the hydrogenolysis of glycerol to
1,3-propanediol was not examined.
As mentioned above, the effect of W loading and calcina-
tion temperature of ­WOx/Al2O3 on the structure and catalytic
performance of Pt-WOx/Al2O3 catalysts is still ambiguous.
Therefore, the motivation for this research was to provide
a better understanding on the influence of the W loading
(10–20 wt.%) and calcination temperatures of ­WOx/Al2O3
(700–900  °C) and Pt-WOx/Al2O3 (350–450  °C) and the
reduction temperature of Pt-WOx/Al2O3 (300–400 °C) on the
transformation of glycerol to 1,3-propanediol. The resulting
Pt-WOx/Al2O3 catalysts were examined using N ­ 2-sorption,
XRD, Raman, CO pulse chemisorption, N ­ H3-TPD, ­H2-TPR,
­H2-TPD, SEM and TEM-EDS and XPS to reveal struc-
ture–activity-selectivity relationships.
2 Experimental
2.1 Catalyst Preparation
2.1.1 Preparation of ­WOx/Al2O3 Supports
WOX/Al2O3 supports containing different amounts of W
(10, 15 and 20 wt.%) were prepared using the impregna-
tion method. In a typical synthesis, the desired amount of
ammonium paratungstate hydrate (Sigma-Aldrich, ≥ 99.99%,
CAS:11120-25-5) was added in 6 mL of deionized water
with stirring at 150 rpm and 60 °C. Subsequent to the com-
plete dissolution, the nanosized alumina support (Sigma-
Aldrich, CAS: 1344-28-1) was put into the solution and
stirred at 150 rpm and 60 °C for 4 h. The obtained product
was dried at 100 °C for 24 h and then calcined at different
temperatures (700, 800 and 900 °C) for 2 h. The heating rate
for all calcination temperatures was 5 °C ­min−1.
2.1.2 Preparation of Pt‑WOx/Al2O3
Pt-WOX/Al2O3 catalysts (5 wt.% Pt) were prepared using
the impregnation method. Briefly, the obtained ­WOx/Al2O3
sample from Sect. 2.1.1 was added in 6 mL of an aqueous
solution consisting of H ­ 2PtCl6·6H2O (CAS:18497-13-7).
The mixture was stirred at 150 rpm and 60 °C for 4 h and
dried at 100 °C for 24 h. The resulting product was calcined
at different temperatures (350 °C, 400 °C and 450 °C) for
4 h with a heating rate of 2 °C ­min−1. The obtained catalysts
were designated as Pt-XW/Al2O3-Y–Z where X, Y, Z are the
W loading content, calcination temperature of W ­ Ox/Al2O3
and calcination temperature of Pt-WOx/Al2O3, respectively.
The Pt-WOx/Al2O3 catalysts prepared with different condi-
tions with their textural properties are listed in Table 1.
Topics in Catalysis (2023) 66:205–222 207

Table 1  Preparation conditions of calcined Pt-WOx/Al2O3 catalysts and their physical properties analyzed using N
­ 2-sorption technique
Catalysts Preparation conditions BET surface Pore volume W surface
area ­(m2 ­g−1) ­(cm3 ­g−1) density (W
W loading Calcination temp. of Calcination temp. of ­nm−2)
(wt.%) ­WOx/Al2O3 (°C) Pt-WOx/Al2O3 (°C)

Pt-10W/Al2O3-800-400 10 800 400 142 0.68 2.31

Pt-15W/Al2O3-800-400 15 800 400 130 0.65 3.78
Pt-20W/Al2O3-800-400 20 800 400 113 0.53 5.80
Pt-15W/Al2O3-700-400 15 700 400 136 0.61 3.61
Pt-15W/Al2O3-900-400 15 900 400 96 0.56 5.10
Pt-15W/Al2O3-800-350 15 800 350 130 0.66 3.78
Pt-15W/Al2O3-800-450 15 800 450 129 0.65 3.81

2.2 Catalyst Characterization 3 Results and Discussion

The textural properties, phase and crystallinity, reducibility, 3.1 Catalyst Characterization

interaction of catalyst surface with H
­ 2, metal compositions,
structure of W­ Ox species, amount and strength of acidic
sites, Pt dispersion and Pt surface area, and surface chem-
istry of Pt species of different catalysts were characterized
using ­N2-physisorption, X-ray diffraction (XRD), tempera-
ture-programmed reduction of ­H2 ­(H2-TPR), temperature-
programmed desorption of ­H2 ­(H2-TPD), transmission elec-
tron microscope and scanning electron microscope equipped
with energy dispersive X-ray spectrometer (TEM-EDS and
SEM-EDS), Raman spectroscopy, temperature-programmed
desorption of ­NH3 ­(NH3-TPD), CO chemisorption and X-ray
photoelectron spectroscopy (XPS), respectively. The details
of catalyst preparation for each technique were given in sup-
plementary material.
2.3 Catalytic Activity Test
The hydrogenolysis of glycerol of all Pt-WOx/Al2O3 cata-
lysts was tested in the liquid phase reaction using a 50 mL
autoclave with an agitator system. The catalyst (0.6 g) was
added into the autoclave and reduced in a pure H ­ 2 flow
(100 mL  ­min−1) at 350 °C for 2 h. After complete reduc-
tion, the reactor temperature was cooled to 50 °C and 30 g
of 10 wt.% glycerol aqueous solution was placed into the
autoclave. The reactor was flushed with a continuous flow
of pure ­N2 for 5 min followed by pure ­H2 for 1 min. Subse-
quently, the reactor was pressurized to 60 bar with pure ­H2
and the reactor was heated to 220 °C with stirring at 600 rpm
and kept at that temperature for 5 h. After the reaction, the
suspension was centrifuged at 8000 rpm for 15 min to sepa-
rate the liquid phase and the solid catalyst. The products
were analyzed according to the procedures described in our
previous work [14] and turn over frequency (TOF) was cal-
culated based on the Equation reported by Jarauta-Córdoba
et al. [23].
Figure 1 displays the effect of W loading contents (10, 15
and 20 wt%), calcination temperatures of W ­ Ox/Al2O3 (700,
800 and 900 °C) and calcination temperatures of Pt-WOx/
Al2O3 (350, 400 and 450 °C) on the N ­ 2-sorption isotherms
and pore size distribution measured using the N ­ 2-sorption
technique. All catalysts exhibited a typical type-IV isotherm
with an H2 hysteresis loop (Fig. 1a), indicating mesoporous
materials with ink-bottle shaped pores. The hysteresis loop
was quite narrow, suggesting that the sizes of the neck-like
and wide body pores were similar. In addition, the hysteresis
loop occurred at a high relative pressure (P/P0~0.95) cor-
responding to the presence of large mesopores (29.2 nm;
Fig. 1b). Both are useful for the fast transport of reactants
and products inside the mesopores. Loading W at 10–15
wt% (Pt-10W/Al2O3-800-400 and Pt-15W/Al2O3-800-400)
did not affect the pore structure but further increasing the
W loading to 20 wt% (Pt-20W/Al2O3-800-400) reduced the
peak intensity significantly, suggesting a partial pore block-
age caused by the growth of ­WOx particles. Increasing the
calcination temperature of ­WOx/Al2O3 from 800 (Pt-15W/
Al2O3-800-400) to 900 °C (Pt-15W/Al2O3-900-400) led to a
reduction of pores in the range 4–20 nm, suggesting the coa-
lescence of tiny particles to form larger particles. The results
corresponded to the substantial reduction in the BET surface
area of the Pt-/20W/Al2O3-800-400 and Pt-15W/Al2O3-900-
400 catalysts (Table 1). Increasing the calcination tempera-
ture (350, 400 and 450 °C) of the Pt-WOx/Al2O3 catalysts
slightly altered pore structures with an almost constant BET
surface area (Table 1). The W surface density, defined as the
number of W atoms per surface area (atom W ­nm−2), was
calculated; the results are shown in Table 1. The W surface
density increased from 2.31 to 5.80 W ­nm−2 with increasing
the W loading content from 10 to 20 wt% and from 3.61 to
5.10 W ­nm−2 with increasing the calcination temperature of
­WOx/Al2O3 from 700 to 900 °C. The W surface density of

13

208
Fig. 1  N2-sorption isotherms of Pt-WOx/Al2O3 prepared with different conditions (a) and their corresponding pore size distribution (b)
the Pt-WOx/Al2O3 catalysts calcined at different tempera-
tures (Pt-15W/Al2O3-800-350, Pt-15W/Al2O3-800-400 and
Pt-15W/Al2O3-800-450) remained unchanged because the
calcination temperatures of the catalysts were much lower
than the calcination temperature of W­ Ox/Al2O3. Notably, the
W surface density (5.8 atom W n­ m−2) at 20 wt% W loading
(Pt-/20W/Al2O3-800-400) was higher than for the monolayer
of W surface density (5.1 atom W n­ m−2) [24] which could
lead to the generation of bulk ­WO3 crystals.
The XRD patterns of the calcined different Pt-WOx/Al2O3
catalysts under air atmosphere are shown in Fig. 2. The XRD
patterns of all catalysts displayed diffraction lines at 2θ val-
ues of 32.80°, 37.64°, 46.60°, 67.25° and 45.85°, 66.85°
which were matched to δ-Al2O3 (PDF 00-046-1131) and
γ-Al2O3 (PDF 00-056-0457), respectively. Small diffrac-
tion lines at 35.92° and 39.49° indexed to the P ­ t3O4 phase
(PDF 00-021-1284) were visible for all catalysts. However,
the peak intensities were quite different depending on the
synthesis conditions. At a low W loading content (10 wt.%,
Pt-10W/Al2O3-800-400), the diffraction line of P ­ t3O4 at
39.49° was clearly observed. Increasing the W loading to
15 (Pt-15W/Al2O3-800-400) and 20 (Pt-20W/Al2O3-800-
400) wt.% led to a significant decrease in the ­Pt3O4 peak
intensity, implying a reduction of P­ t3O4 crystallite size or a
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Topics in Catalysis (2023) 66:205–222
strong metal-support interaction. However, the significant
reduction of BET surface area of the Pt-20W/Al2O3-800-
400 sample compared to the Pt-10 W/Al2O3-800-400 sample
(Table 1) indicated that there was a strong Pt-W interac-
tion and thus the diffraction line of P­ t3O4 was not clearly
visible. The diffraction lines of the ­WO3 crystalline phase
(PDF 01-075-2187) were visible for the Pt-20W/Al2O3-800-
400 sample, indicating the formation of bulk W ­ O3 crystals,
which was in line with its W surface density value (Table 1).
The XRD pattern of Pt-15W/Al2O3-700-400 was similar
to that of Pt-15 W/Al2O3-800-400, suggesting that crystal
structure of metal oxides did not change with an increase
in the calcination temperature of W ­ Ox/Al2O3 from 700 °C
(Pt-15W/Al2O3-700-400) to 800 °C (Pt-15W/Al2O3-800-
400). The XRD pattern of Pt-15W/Al2O3-900-400 remained
unaltered compared to that of Pt-15W/Al2O3-800-400 and
Pt-15W/Al2O3-700-400, even though the calcination tem-
perature increased to 900 °C and its BET surface area was
26.1% lower than that of the 15W/Al2O3-800-400 sample.
This affirmed that the presence of a strong Pt-W interaction
promoted the dispersion of Pt oxides species. The XRD pat-
tern of Pt-15W/Al2O3-800-350 exhibited a diffraction line
of ­PtCl2, suggesting that a calcination temperature of Pt-
WOx/Al2O3 at 350 °C was insufficient to decompose ­PtCl2
Topics in Catalysis (2023) 66:205–222 209
Fig. 2  XRD patterns of calcined Pt-WOx/Al2O3 catalysts prepared
with different conditions
crystal. The diffraction line of ­PtCl2 was not observed for
15W/Al2O3-800-400 sample. Further increasing calcination
temperature to 450 °C (Pt-15W/Al2O3-800-450) tended to
enlarge the ­Pt3O4 crystallite sizes. TEM-EDS analysis was
used to examine the dispersion of Pt and the presence of
Cl in the catalysts calcined at 350 °C (Pt-15W/Al2O3-800-
350) and 400 °C (Pt-15W/Al2O3-800-400); the results are
shown in Figs. 3 and 4, respectively. It was found that Pt
was highly dispersed throughout the surface of both cata-
lysts and the Cl/Pt mass ratio of Pt-15W/Al2O3-800-350 was
found to be 0.161 which was 1.45 times higher than that
of Pt-15W/Al2O3-800-400. The metal compositions of all
catalysts were further investigated with SEM-EDS analysis.
As shown in Table 2, the metal compositions of all catalysts
were closed to their expected ratios. In addition, the Cl/Pt
mass ratio of Pt-WOx/Al2O3 at 350 °C was also higher than
that of the other catalysts which was in good agreement with
TEM-EDS analysis. The higher Cl/Pt mass ratios of Pt-15W/
Al2O3-800-350 was likely associated with the remaining
small ­PtCl2 crystals as observed by XRD analysis (Fig. 2).
Figure 5a shows the Raman spectra of A ­ l2O3 calcined
at 800 °C ­(Al2O3-800), Pt-Al2O3 calcined at 400 °C (Pt-
Al2O3-800-400), W/Al2O3 with 15 wt% (15W/Al2O3-800)
and 20 wt% (20W/Al2O3-800) tungsten loading content. No
significant band was observed for the A ­ l2O3-800. The Pt-
Al2O3-800-400 exhibited a strong band at 590 ­cm−1 and a
small band at 335 ­cm−1 which were reported to be a charac-
teristic of highly dispersed P ­ tOx on A­ l2O3 [25]. Loading 15
wt.% tungsten on A ­ l2O3 (15W/Al2O3-800) showed a strong
band at 989 ­cm−1 attributable to ʋ(W = O) vibrations of pol-
ytungstate species [23, 26]. Additional three small bands at
271, 690 and 809 ­cm−1 assigned to crystal structure of W ­ O3
[23, 26] were visible when the tungsten loading content was
raised to 20 wt% (20W/Al2O3-800), suggesting an initial
stage in the crystalline ­WO3 formation.
After impregnation of Pt onto ­WOx/Al2O3 (Fig. 5b–d),
the Raman spectra showed a combination of bands of both
polytungstate species and amorphous P ­ tOx but the bands
intensity were different depending on the synthesis condi-
tions. As shown in Fig. 5b, the band at 974 ­cm−1 increased
with increasing W loading from 10 to 20 wt%. However,
the bands representative for crystalline W ­ O 3 were not
clearly observed as those of 20W/Al2O3-800, possibly due
to a strong interaction of Pt with W species [27]. Similarly,
the band intensity of polytungstate species increased with
increasing calcination temperature of ­WOx/Al2O3 (Fig. 5c)
from 700 to 900 °C, suggesting an increase of surface den-
sity of polytungstate. The different calcination temperatures
(350 °C, 400 °C, and 450 °C) of Pt-WOx/Al2O3 catalysts also
affected the surface structure of catalysts. Only small band
at 578 ­cm−1 was visible for the catalyst calcined at 350 °C
(Pt-15W/Al2O3-800-350), which might be attributed to the
incomplete decomposition of H ­ 2PtCl6. At 450 °C (Pt-15W/
Al2O3-800-450), the band of ­PtOx became more predomi-
nant than the band of polytungstate, suggesting that amor-
phous ­PtOx aggregated to form a larger size covering the
surface of polytungstate.
The reduction behavior of the different Pt-WOx/Al2O3
catalysts as well as Pt/Al2O3 is presented in Fig. 6. The
­H2-TPR profile of Pt/Al2O3 (in the absence of ­WOx) exhib-
ited a main H ­ 2 consumption peak at 150 °C and a broad peak
at 595 °C that could be attributed to a reduction of ­Pt3O4
to metallic Pt and a reduction of P ­ tOx strongly interacted
with ­Al2O3, respectively. The reduction behavior of ­Pt3O4
was noticeably changed when W ­ Ox was present in the Pt-
WOx/Al2O3 system. All Pt-WOx/Al2O3 catalysts displayed
two main steps of H ­ 2 consumption (at 75 °C and 150 °C)
that could be assigned to a reduction of ­Pt3O4 dispersed on
­WOx and a reduction of P ­ t3O4 on A­ l2O3, respectively. The
­H2 consumption at temperatures > 200 °C could be attributed
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210 Topics in Catalysis (2023) 66:205–222

Fig. 3  TEM-EDS mapping of Pt-15 W/Al2O3-800-350

Fig. 4  TEM-EDS mapping of Pt-15 W/Al2O3-800-400

13
Topics in Catalysis (2023) 66:205–222 211

Table 2  Metal compositions Samples Metal compositions (wt%) Cl/Pt ratio

measured by SEM–EDS and
TEM-EDS analysis of all Pt W Al O Cl Catalystsa H2PtCl6·6H2O
calcined catalysts
Pt-10W/Al2O3-800-400 4.20 8.46 34.58 52.35 0.41 0.10 1.09
Pt-15W/Al2O3-800-400 4.54 13.48 36.15 45.33 0.50 0.11
(0.11)
Pt-20W/Al2O3-800-400 5.45 16.78 33.36 43.79 0.62 0.11
Pt-15W/Al2O3-700-400 4.74 13.15 38.04 43.53 0.54 0.11
Pt-15W/Al2O3-900-400 4.62 13.65 36.14 45.08 0.51 0.11
Pt-15W/Al2O3-800-350 4.06 13.51 32.77 48.79 0.87 0.21
(0.16)
Pt-15W/Al2O3-800-450 6.16 12.91 31.53 48.78 0.62 0.10
a
 The values in parenthesis were obtained with TEM-EDS analysis

to a reduction of ­WOx species and that is the reason why the
­H2-TPR profiles of the Pt-WOx/Al2O3 catalysts do not return
to the baseline similar to the Pt/Al2O3 catalyst. This phenom-
enon was also observed from the other groups using Pt/WOx
based catalysts [27, 28]. The reduction of W ­ Ox species can
be easier when the Pt was present because the H ­ 2 could dis-
sociate over the Pt surface and then spillover to reduce W ­ Ox
species. Compared to the Pt-10W/Al2O3-800-400 sample
(Fig. 6a), the Pt-15 W/Al2O3-800-400 and Pt-/20W/Al2O3-
800-400 samples had a smaller ­H2 consumption at 150 °C
but a larger ­H2 consumption at > 200 °C, indicating that a
larger fraction of ­PtOx of Pt-15W/Al2O3-800-400 and Pt-
/20W/Al2O3-800-400 was in close proximity to the surface
of ­WOx compared to Pt-10W/Al2O3-800-400 sample. The
­H2 consumption over W ­ Ox/Al2O3 calcined at 700 °C (Pt-
15W/Al2O3-700-400) was lower than that of ­WOx/Al2O3
calcined at 800 °C (Pt-15W/Al2O3-800-400) and 900 °C
(Pt-15W/Al2O3-900-400), indicating that increasing the cal-
cination temperature allowed the W ­ Ox surface to be more
reducible (Fig. 6b). When the synthesized Pt-WOx/Al2O3
was pre-calcined at 350 °C (Pt-15W/Al2O3-800-350), the
reduction behavior at 0–150 °C did not resemble that of the
synthesized catalysts pre-calcined at 400 °C (Pt-15W/Al2O3-
800-400) which could be attributed to the reduction of P ­ tCl2.
A slight decrease in the ­H2 consumption was observed when
the calcination temperature of Pt-WOx/Al2O3 increased to
450 °C (Pt-15W/Al2O3-800-450) which was associated with
a sintering of Pt particles (Fig. 6c).
Figure 7 shows the XRD patterns of the Pt-WOx/Al2O3
catalysts reduced with H ­ 2 at 350 °C for 2 h. The XRD pat-
tern of Pt-10W/Al2O3-800-400 displayed a prominent dif-
fraction line of metallic Pt, suggesting the presence of iso-
lated Pt particles with a low interfacial contact with W ­ Ox
species. The peak intensity of metallic Pt became smaller as
the W loading content increased from 10 wt% to 15 wt% (Pt-
15W/Al2O3-800-400) and 20 wt% (Pt-20W/Al2O3-800-400),
confirming a strong affinity of the Pt and W species. The
diffraction lines of ­WO3 still remained in the XRD pattern of
the Pt-20W/Al2O3-800-400 sample but their peaks were not
clearly seen due to a partial reduction of bulk ­WO3 promoted
by metallic Pt. Similar to the increase in the W loading con-
tent, the metallic Pt peak intensity notably decreased when
the calcination temperature increased from 700 to 900 °C,
suggesting a strong Pt-W interaction when the ­WOx/Al2O3
sample was calcined at > 700 °C. Some P ­ tCl2 species still
existed on the surface of the Pt-WOx/Al2O3 catalyst pre-
calcined at 350 °C followed by reduction at 350 °C (Pt-15W/
Al2O3-800-350). The XRD technique could not distinguish
the crystal structure when the calcination temperature of Pt-
WOx/Al2O3 increased from 400 °C (Pt-15W/Al2O3-800-400)
to 450 °C (Pt-15W/Al2O3-800-450). In addition, the effect
of reduced temperature was studied by reducing the Pt-15W/
Al2O3-800-400 sample at 300 °C (Pt-15W/Al2O3-800-400
reduced at 300 °C) and 400 °C (Pt-15W/Al 2O3-800-400
reduced at 400 °C) for 2 h. Clearly, increasing the reduction
temperature to 400 °C caused mobility of Pt particles to
form a larger Pt particle size.
The temperature programmed desorption (TPD) of ­H2
was conducted to gain further insight into the structure of
Pt-WOx/Al2O3 catalysts prepared at different conditions. The
­H2-TPD profiles of all Pt-WOx/Al2O3 catalysts exhibited two
main desorption peaks. The low-temperature desorption fea-
ture (50–200 °C) was attributed to the desorption of atomic
H over the metallic Pt surface and oxygen vacancies of at
the Pt-supports ­(WOx and ­Al2O3) interface [29, 30], while
the high-temperature desorption feature (250–600 °C) could
be attributed to the spillover of H atom to the surface of
­Al2O3 and partially reduced ­WOx [30, 31]. The area under
the low-temperature peak of the Pt-10W/Al2O3-800-400
sample (10 wt.% W loading) was the lowest in the series of
effects of the W loading content (Fig. 8a), possibly due to
the larger Pt crystallite size and lower interfacial contact of
Pt and supports. The area under the low-temperature peak of
Pt-20W/Al2O3-800-400 sample was slightly lower than that
of the Pt-15W/Al2O3-800-400 sample due to the formation
of crystalline ­WO3, resulting in the significant drop in the

13

212
Fig. 5  Raman spectra of ­ Al2O3 calcined at 8­00oC ­(Al2O3-800),
Pt-Al2O3 calcined at 400 oC (Pt-Al2O3-800-400),  ­WOx loaded on
­Al2O3 with 15 wt% W loading (15W/Al2O3-800) and 20 wt% W load-
ing (20W/Al2O3-800)  (a) and Pt-WOx/Al2O3  catalysts prepared with
different conditions including Pt-10W/Al2O3-800-400 (A), Pt-15W/
BET surface area which could lead to a lower dispersion of
Pt compared to that of the Pt-15W/Al2O3-800-400 sample.
Figure 8b shows the H­ 2-TPD profiles of the Pt-WOx/Al2O3
catalysts prepared with different calcination temperatures
13
Topics in Catalysis (2023) 66:205–222
Al2O3-800-400 (B), Pt-20W/Al2O3-800-400 (C), Pt-15W/Al2O3-700-
400 (D), Pt-15W/Al2O3-900-400 (E), Pt-15W/Al2O3-800-350 (F) and
Pt-15W/Al2O3-800-450 (G).  The meaning of the catalysts' relative
notation is given in Table 1
of ­WOx/Al2O3. At 700 °C (Pt-15W/Al2O3-700-400), the
areas under both the low- and high-temperature features
were substantially lower than those of Pt-15W/Al2O3-800-
400, suggesting the low Pt-support interfaces as well as the
Topics in Catalysis (2023) 66:205–222 213
Fig. 6  H2-TPR profiles of different Pt-WOx/Al2O3 catalysts and Pt/Al2O3: Pt-WOx/Al2O3 catalysts prepared with different W loading contents
(a), with different calcination temperatures of W
­ Ox/Al2O3 (b) and with different calcination temperatures of Pt-WOx/Al2O3 (c)
Fig. 7  XRD patterns of reduced Pt-WOx/Al2O3 catalysts prepared
with different conditions
less reducible W­ Ox species (Fig. 8b). At 900 °C (Pt-15W/
Al2O3-900-400), the area under high-temperature increased,
suggesting an increase in the reducible ­WOx species.
The calcination temperature of the Pt-WOx/Al2O3 cata-
lysts also affected the amount of H ­ 2 absorbed. As shown
in Fig. 8c, at 350 °C (Pt-15W/Al2O3-800-350), both des-
orption peaks were lower than for the Pt-15W/Al2O3-800-
400 catalyst possibly due to the loss of Pt active surface. At
450 °C (Pt-15W/Al2O3-800-450), the low-temperature peak
substantially dropped compared to that of Pt-15W/Al2O3-
800-400, suggesting sintering of the Pt particles. The effect
of the reduction temperature of the Pt-15W/Al2O3-800-400
catalyst is presented in Fig. 8d. At 300 °C, the area under the
low-temperature feature was the smallest in the series which
could be attributed to the remaining ­PtOx species. Increasing
the reduction temperature to 400 °C caused a slight decrease
in the area under the low-temperature feature, probably due
to mobility of the Pt particles on the catalyst surface to form
a larger particle at such a reduction temperature. Clearly, the
high-temperature feature peak shifted toward a higher des-
orption temperature as the reduction temperature increased,
suggesting a strengthened interaction of H with the W ­ Ox
surface.
The CO pulse chemisorption was used to determine
the Pt surface area and Pt dispersion of different Pt-WO x/
Al2O3 catalysts. As can be seen in Table 3, the Pt surface
area and dispersion of all catalysts were greatly differ-
ent despite they have the same amount of Pt loading (5
wt%). At W loading of 10 wt% (Pt-10W/Al2O3-800-400),
the Pt dispersion had the highest value of 52.6%. The Pt
dispersion was found to be 31.9% and 16.2% when the W
13

214 Topics in Catalysis (2023) 66:205–222

Fig. 8  H2-TPD profiles of dif-

ferent Pt-WOx/Al2O3 catalysts:
effect of W loading contents (a)
effect of calcination tempera-
tures of ­WOx/Al2O3 (b), effect
of calcination temperatures of
Pt-WOx/Al2O3 (c) and effect of
reduction temperatures of Pt-
WOx/Al2O3 (d)

Table 3  Acidity of pre-reduced Pt-Al2O3 and Pt-WOx/Al2O3 catalysts determined by N

­ H3-TPD measurement and Pt surface area and its disper-
sion determined by CO pulse chemisorption
Samples Amount of acid sites (mmol ­g−1) Pt surface area Pt dis-
­(m2 ­g−1) persion
Weak I (τ) Weak II (β) Medium (α) Strong (γ) Total acid sites (%)

Pt-Al2O3 – 0.157 0.031 – 0.188 – –

Pt-10W/Al2O3-800-400 0.024 0.180 0.136 0.090 0.430 6.49 52.6
Pt-15W/Al2O3-800-400 0.018 0.179 0.182 0.132 0.511 3.94 31.9
Pt-20W/Al2O3-800-400 0.028 0.143 0.189 0.110 0.470 2.01 16.2
Pt-15W/Al2O3-700-400 0.021 0.163 0.173 0.092 0.449 4.29 34.7
Pt-15W/Al2O3-900-400 0.027 0.185 0.218 0.150 0.580 2.86 23.1
Pt-15W/Al2O3-800-350 0.022 0.141 0.158 0.102 0.423 1.89 15.3
Pt-15W/Al2O3-800-450 0.023 0.132 0.168 0.088 0.411 3.02 24.5

13
Topics in Catalysis (2023) 66:205–222 215
loading content increased to 15 (Pt-15W/Al2O3-800-400)
and 20 (Pt-20W/Al 2O3-800-400) wt%, respectively. The
Pt dispersion decreased from 34.7 to 23.1% with rais-
ing calcination temperature of W ­ O x/Al 2O 3 from 700 to
900 °C. Based on the results of XRD of reduced catalysts
(Fig. 7), and CO pulse chemisorption, the CO molecules
selectively adsorbed on the isolated Pt particles, while the
interface of Pt-supports were inactive on CO adsorption.
The Pt dispersion over the Pt-WO x/Al 2O 3 catalyst cal-
cined at 350 °C was found to be the lowest value (15.3%).
The Pt dispersion increased to 31.9% when the calcination
temperature of the Pt-WO x/Al 2O 3 catalyst increased to
400 °C (Pt-15W/Al2O3-800-400). Further increase of cal-
cination temperature to 450 °C (Pt-15W/Al2O3-800-450)
caused a significant drop in the Pt dispersion to 24.5%.
The acid strength and number of acidity of the Pt-
Al 2O 3 and different Pt-WO x/Al 2O 3 catalysts were eval-
uated by N ­ H 3-TPD technique. As shown in Fig. 9, the
­N H 3-TPD profile of Pt-Al 2O 3 catalyst exhibited a main
desorption peak at 236 °C with a shoulder at 333 °C, sug-
gesting that the Pt-Al2O3 catalyst mainly contained weak
acidity corresponding to the presence of A ­ l + as Lewis
acid sites. The presence of tungsten on Pt-Al2O3 catalysts
remarkably enhanced the medium and strong acid sites.
The number of acidities for each acid site was summa-
rized in Table 3. It was found that the medium acid sites
Fig. 9  NH3-TPD profiles of
Pt-Al2O3 and different Pt-WOx/
Al2O3 catalysts
increased with increasing tungsten loading content and
calcination temperature of ­WOx/Al2O3.
3.2 Catalyst Activity Test
The catalytic performance of the Pt-WOx/Al2O3 catalysts
with different conditions for hydrogenolysis of glycerol is
displayed in Figs. 10–13. As shown in Fig. 10a, Pt/Al2O3
catalyst in the absence of W gave a low glycerol conversion
of 14.0% and the glycerol was mostly converted to 1,2-pro-
panediol (Fig. 10b). The Pt-WOx/Al2O3 catalyst with 10
wt.% W loading (Pt-10W/Al2O3-800-400) provided a higher
glycerol conversion of 36.5% with a significant improvement
of 1,3-propanediol selectivity from 3.5 to 36.8%, suggest-
ing that the presence of medium acid sites (Fig. 9) after the
tungsten addition altered the product selectivity. Increasing
the W loading content to 15 wt.% (Pt-15W/Al2O3-800-400)
notably improved the glycerol conversion to 44.7% as well as
1,3-propanediol selectivity (45.1%). The propanol selectivity
also increased to 26.8% with increasing the W loading con-
tent to 15 wt.%. A further increase of the W loading content
to 20 wt.% (Pt-20W/Al2O3-800-400) led to a slight reduction
in both glycerol conversion (Fig. 10a) and 1,3-propanediol
selectivity (Fig. 10b).
In addition to the medium acid sites, previous works
have shown that the type of acid site (Lewis and Brønsted)
determined the product’s selectivity toward 1,2-propanediol
13

216
Fig. 10  Effect of W loading contents on conversion and yield (a), product selectivity (b) and proposed structures of Pt-WOx/Al2O3 catalysts (c)
and 1,3-propanediol, respectively [2]. Aihara et al. [32]
found that no 1,3-propanediol was formed over a Pt/Al2O3
catalyst as it contained mainly Lewis acid sites. Increasing
the Brønsted-to-Lewis acid ratio shifted the selectivity of
products toward 1,3-propanediol [21]. Based on the catalyst
characterization and previous reports, the low 1,3-propan-
ediol selectivity over the Pt-10W/Al2O3-800-400 catalyst
(10 wt.% W loading) in the current study was attributed
to the low density of W­ Ox groups forming slight bridging
W-O-W bonds, yielding a small fraction of Brønsted acid
sites. Increasing the W loading content to 15 wt.% (Pt-15W/
Al2O3-800-400) created more bridging W–O-W bonds that
could delocalize electrons entirely partially reduced ­WOx
domains [33, 34]. The delocalized electrons over the par-
tially reduced ­WOx domains were essential to stabilize ­Hδ+
acting as Brønsted acid sites (Fig. 10c). A further increase
in the W loading content to 20 wt.% (Pt-20W/Al2O3-800-
400) led to the formation of an inactive W
­ O3 phase, resulting
in a slight drop in 1,3-propanediol and propanol selectivi-
ties. Note that further catalysts analysis with in situ FTIR
technique with pyridine should be carried out to affirm the
Brønsted-to-Lewis acid ratio [23].
13
Topics in Catalysis (2023) 66:205–222
The effect of the calcination temperature of ­WOx/Al2O3
on the catalytic performance for the hydrogenolysis of glyc-
erol is presented in Fig. 11. The Pt-15W/Al2O3-700-400
sample gave the lowest glycerol conversion of 37.2% and the
highest 1,2-propanediol selectivity of 32.5% in the series.
Increasing the calcination temperature to 800 °C (Pt-15W/
Al2O3-800-400) increased the glycerol conversion to 44.7%
as well as producing a substantial reduction in the 1,2-pro-
panediol selectivity to 27.1%, accompanied by an increase
in 1,3-propanediol selectivity to 45.1%. At 900 °C (Pt-15W/
Al2O3-900-400), both the conversion of glycerol (Fig. 11a)
and 1,3 propanediol selectivity (Fig. 11b) dropped slightly.
The XRD and ­H2-TPD analyses (Figs. 7 and 8b) of the
reduced Pt-15W/Al2O3-700-400 sample indicated the weak-
ened interaction of the Pt and ­WOx species and low hydro-
gen spillover ability which resulted in more difficulty reduc-
ibility of the W ­ δ+. In addition, the
­ Ox surface to generate H
high Pt dispersion (34.7%) but low interfacial contact of
­WOx species with Pt implied that part of Pt was dispersed
on ­Al2O3 support which provided a low glycerol conversion
as well as high 1,2-Propanediol selectivity. At 900 °C (Pt-
15W/Al2O3-900-400), more W-O-W bonds were linked to
each other to form a large ­WOx domain (Fig. 11c), favoring
Topics in Catalysis (2023) 66:205–222 217
Fig. 11  Effect of calcination temperatures of ­WOx/Al2O3 on conversion and yield (a), product selectivity (b) and proposed structures of Pt-WOx/
Al2O3 catalysts (c)
the formation of Brønsted acid sites and promoting the
production of 1,3-propanediol. However, the selectivity of
1,3-propanediol of the Pt-15W/Al2O3-900-400 catalyst was
slightly lower than for the Pt-15W/Al2O3-800-400 catalyst
but enhancement of propanol selectivity was observed that
was attributed to over-hydrogenation of 1,3-propanediol to
propanol due to more available H over the ­WOx surface, as
confirmed by the ­H2-TPD analysis (Fig. 8b).
Figure 12 shows the effect of the calcination tempera-
ture of Pt-WOx/Al2O3 while maintaining the calcination
temperature of W­ Ox/Al2O3 at 800 °C. Clearly, the conver-
sion of glycerol over the Pt-WOx/Al2O3 calcined at 350 °C
(Pt-15W/Al2O3-800-350) was only 30.9%, which was much
lower than for the Pt-15W/Al2O3-800-400 sample (44.7%).
In addition, the product selectivity levels of both catalysts
were quite different, as the Pt-15W/Al2O3-800-350 sample
predominantly gave 44.3% 1,2-propanediol selectivity, while
the highest product selectivity over the Pt-15W/Al2O3-800-
400 sample was altered to 1,3-propanediol (45.1%). In fact,
the calcination temperature of ­WOx/Al2O3 of both catalysts
was identical, providing similar ­WOx coverage on ­Al2O3.
Therefore, the low activity and selectivity of 1,3-propan-
ediol were mainly attributed to the phase of the Pt species
(Fig. 12c). Based on the XRD analysis of the reduced Pt-
15W/Al2O3-800-350 sample (Fig. 7), ­PtCl2 species still
remained in the structure of the catalysts. Although P ­ tCl2
has been reported to be active for methane oxidation to
methyl bisulfate [35, 36], this phase could have been inac-
tive for the dissociation of ­H2, retarding the formation of
­Hδ+ and the hydrogenation ability of the catalyst. Increasing
the calcination temperature of the Pt-WOx/Al2O3 catalyst to
450 °C (Pt-15W/Al2O3-800-450) led to a slight decrease in
glycerol conversion and 1,3-propanediol and propanol selec-
tivities to 43.7%, 41.2% and 26.1%, respectively, compared
to 44.7%, 45.1% and 26.8%, respectively, of the Pt-15W/
Al2O3-800-400 sample which were likely associated with a
partial sintering of Pt particles (Fig. 12c).
Figure 13 shows the effect of reduction temperatures
of Pt-WOx/Al2O3 catalysts calcined at 400 °C. The low-
est glycerol conversion and 1,3-propanediol and propanol
selectivities of 29.1%, 31.2% and 16.9%, respectively, were
achieved over the Pt-15W/Al2O3-800-400 catalyst reduced
13

218
Fig. 12  Effect of calcination temperatures of Pt-WOx/Al2O3 on conversion and yield (a), product selectivity (b) and proposed structures of Pt-
WOx/Al2O3 catalysts (c)
at 300 °C. These values were notably lower than the Pt-15W/
Al2O3-800-400 catalyst reduced at 350 °C even though the
calcination temperatures of both samples during the prepa-
ration of W­ Ox/Al2O3 and Pt-WOx/Al2O3 were identical,
suggesting similar W surface densities. Therefore, the low
glycerol conversion and 1,3-propanediol and propanol selec-
tivities over the Pt-15W/Al2O3-800-400 catalyst reduced at
300 °C were likely associated with an incomplete reduction
of ­PtOx to metallic Pt (Fig. 13c), lowering the capability for
­H2 dissociation and the number of ­Hδ+ on the ­WOx domain,
resulting in a decrease in active sites for the generation of
1,3-propanediol as well as propanol. Further increasing
the reduction temperature to 400 °C resulted in a slightly
lower glycerol conversion and 1,3-propanediol selectivity
compared to those of the Pt-15W/Al2O3-800-400 sample,
probably due to a slight growth of Pt particles and the too
strong interaction of H with the W
­ Ox surface, as indicated by
the ­H2-TPD analysis (Fig. 8d). XPS analysis was performed
to investigate the surface Pt species after reduction with H­ 2
at different temperatures (Fig. 14). The calcined Pt-15W/
Al2O3-800-400 catalyst exhibited two peaks at 316.2 and
13
Topics in Catalysis (2023) 66:205–222
333.7 eV, belonging to Pt ­4d5/2 and Pt ­4d3/2, respectively,
that were then shifted toward lower binding energies at 315.5
and 332.1 eV, respectively, and 315.3 and 331.9 eV, respec-
tively, when the Pt-15W/Al2O3-800-400 catalyst reduced
at 300 and 350 °C, respectively. The position of the Pt 4d
XPS spectra changed slightly with a further increase in the
reduction temperature to 400 °C. The results suggested that
the reduction of ­Pt3O4 was incomplete at 300 °C, which was
attributed to the low activity and selectivity of the catalyst
(Fig. 13).
Figure 15a shows the T­ OF1,3-PDO-W as a function of Pt dis-
persion and W surface density. A linear correlation between
­TOF1,3-PDO-W and Pt dispersion was observed except that of
Pt-10W/Al2O3-800-400 sample and Pt-15W/Al2O3-700–400
sample due to the lower amount of tungsten and different
tungsten species, respectively. The latter could be related
to the significant reduction of H atom adsorbed on partially
reduced ­WOx as observed by H ­ 2-TPD analysis (Fig. 8b).
These findings were analogous with the recent study
reported by Jarauta-Córdoba et al. [23]. The relationship
between ­TOF1,3-PDO-W and W surface density did not clearly
Topics in Catalysis (2023) 66:205–222 219
Fig. 13  Effect of reduction temperatures of Pt-WOx/Al2O3 on conversion and yield (a), product selectivity (b) and proposed structures of Pt-
WOx/Al2O3 catalysts (c)
emanate in this study (Fig. 15b). For example, the Pt-WOx/
Al2O3 catalysts calcined at 350 °C to 450 °C had almost the
same W surface density but the ­TOF1,3-PDO-W differed which
was likely associated with Pt species and Pt dispersion. Nev-
ertheless, it could be seen that the maximum ­TOF1,3-PDO-W
was found at W surface density of 3.78 W ­nm−2 which was
lower than a theoretical monolayer coverage of ­WOx spe-
cies (5.1 W ­nm−2). The similar result was also observed by
Jarauta-Córdoba et al. [23] and it was suggested that glyc-
erol was adsorbed and activated on W ­ δ+–O–Al interface.
However, we also found that the decline in ­TOF1,3-PDO-W
after the W surface density of 3.78 W ­nm−2 was also related
to the reduction of Pt dispersion (Fig. 15a). Further in situ
characterization of Pt-WOx/Al2O3 catalysts is essential to
confirm the active sites and mechanism for hydrogenolysis
of glycerol to 1,3-propanediol.
4 Conclusions
The present study revealed the structure-activity relation-
ships of Pt-WOx/Al2O3 catalysts prepared with different W
loading contents and pretreatment conditions (calcination
temperatures of ­WOx/Al2O3, calcination temperature of Pt-
WOx/Al2O3 and reduction temperature of Pt-WOx/Al2O3) for
the hydrogenolysis of glycerol to 1,3-propanediol. There was
a synergistic effect of Pt and W
­ Ox as the Pt particles were
highly dispersed with increasing W loading content. The
optimum W loading content was 15%, which was sufficient
to create W-O-W clusters providing the delocalization of
electrons to stabilize H atom spillover from the Pt surface.
The calcination temperature of ­WOx/Al2O3 engaged the dis-
persion of W­ Ox species over the A ­ l2O3 surface, with the
­WOx/Al2O3 calcined 700 °C offering high dispersion of W
species, due to the negative effect on the formation of ­Hδ+
over the ­WOx domain as the surface of highly dispersed
­WOx (isolated ­WOx) was hardly reduced. The calcination
temperature of ­WOx/Al2O3 at 800 °C allowed the connection
of each isolated W­ Ox group to form W-O-W clusters that
13

220 Topics in Catalysis (2023) 66:205–222

was related to the maximum glycerol conversion (44.7%)

and 1,3-propanediol selectivity (45.1%). After impregna-
tion of ­WOx/Al2O3 with a Pt precursor (­ H2PtCl6 ­(H2O)6),
an ample calcination temperature at 400 °C was essential
to decompose the Pt precursor. The reduction temperature
of the Pt-WOx/Al2O3 catalysts at 350 °C was adequate to
achieve the active and selective Pt-WOx/Al2O3 catalysts for
glycerol conversion to 1,3-propanediol.

Supplementary Information  The online version contains supplemen-

tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 11244-0​ 22-0​ 1753-9.

Acknowledgements  This work was financially supported by the

Kasetsart University Research and Development Institute (KURDI),
(FF(KU)21.65).

Author Contributions  ND: investigation, writing-reviewing and edit-

ing. TN: investigation, validation, writing-original draft preparation,
writing-reviewing and editing. CW: visualization, writing-reviewing
and editing. AS: visualization, writing-reviewing and editing. KF:
visualization, writing-reviewing and editing. CKC: visualization,
writing-reviewing and editing. D-VNV: visualization, writing-review-
ing and editing. SN: visualization, writing-reviewing and editing. NC:
visualization, writing-reviewing and editing. TW: conceptualization,
methodology, writing-original draft preparation, writing-reviewing and
editing.

Fig. 14  Pt 4d XPS spectra of calcined Pt-15  W/Al2O3-800-400 and Data availability  Authors can confirm that all relevant data are included
Pt-15 W/Al2O3-800-400 reduced at 300, 350 and 400 °C in the article and/or its supplementary information files.

Fig. 15  TOF1,3-PDO-W as a function of Pt dispersion (a) and W surface density (b). Operating conditions: 220 °C, 60 bar, reaction time of 5 h and
10 wt.% glycerol aqueous solution

13
Topics in Catalysis (2023) 66:205–222 221
Declarations  14. Numpilai T, Cheng CK, Seubsai A, Faungnawakij K, Limtrakul
Conflict of interest  The authors declare that they have no conflicts of
interest.
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