Selective hydrodeoxygenation of lignin-related 4-propylphenol into n-propylbenzene in water by Pt-Re/ZrO2 catalysts

Article abstract of DOI:10.1016/j.cattod.2014.01.022

Bimetallic Pt-Re/ZrO₂ catalysts were developed for the selective hydrodeoxygenation of 4-propylphenol as a lignin model to n-propylbenzene in water. The addition of Re to Pt/ZrO₂ improved the catalyst stability and product selectivity. Reaction temperature greatly affected not only reaction efficiency but also product distribution. n-Propylbenzene was obtained in up to 73% yield with ca. 80% selectivity. After the reaction, the catalyst was deactivated possibly due to water-induced wrapping of Pt nanoparticles in ZrO₂. The reaction may involve the hydrogenation of 4-propylphenol to 4-propylcyclohexanol, followed by the dehydration to give 4-propylcyclohexene and the subsequent dehydrogenation to n-propylbenzene.

Full text of DOI:10.1016/j.cattod.2014.01.022

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Catalysis Today
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Selective hydrodeoxygenation of lignin-related 4-propylphenol into
n-propylbenzene in water by Pt-Re/ZrO catalysts
2
Hidetoshi Ohtaa,b, Bo Feng , Hirokazu Kobayashi , Kenji Hara , Atsushi Fukuoka
a
a
a
a,∗
a
Catalysis Research Center, Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan
Department of Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577,
b
Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Bimetallic Pt-Re/ZrO2 catalysts were developed for the selective hydrodeoxygenation of 4-propylphenol
as a lignin model to n-propylbenzene in water. The addition of Re to Pt/ZrO2 improved the catalyst sta-
bility and product selectivity. Reaction temperature greatly affected not only reaction efficiency but also
product distribution. n-Propylbenzene was obtained in up to 73% yield with ca. 80% selectivity. After the
reaction, the catalyst was deactivated possibly due to water-induced wrapping of Pt nanoparticles in ZrO2.
The reaction may involve the hydrogenation of 4-propylphenol to 4-propylcyclohexanol, followed by the
dehydration to give 4-propylcyclohexene and the subsequent dehydrogenation to n-propylbenzene.
Received 8 November 2013
Received in revised form 17 January 2014
Accepted 22 January 2014
Available online xxx
Keywords:
Biomass
Hydrodeoxygenation
Lignin model
Aromatic hydrocarbon
Pt catalyst
©
2014 Elsevier B.V. All rights reserved.
Water
1
. Introduction
the HDO of lignin and related chemicals into aromatic hydrocar-
bons.
The use of renewable biomass for the synthesis of petrochemi-
Aqueous-phase HDO of phenols has been extensively inves-
tigated in recent years [22–26]. This process is suitable for the
conversion of water-containing lignin-related chemicals, and the
easy separation of the organic products from the aqueous phase is
cals is crucial to reduce the dependency on limited reserves of fossil
fuels [1–4]. Due to the structure and availability, lignin is considered
as a promising resource of aromatic hydrocarbons which are indus-
trially important feedstock for producing a wide variety of useful
chemicals such as polymers, pharmaceuticals, agrochemicals and
electronic chemicals [5]. Hydrodeoxygenation (HDO) is an impor-
tant technology for upgrading of lignin and related chemicals into
aliphatic [6–9] and aromatic hydrocarbons [10–16]. For the synthe-
sis of aromatic hydrocarbons, conventional sulfided CoMo catalysts
show good activity [17–19]; however, they suffer from the deacti-
vation caused by coke formation and in-situ generated water in
the HDO reaction [20]. Ni/SiO2 was developed for the gas-phase
conversion of phenol to benzene in mixed aqueous/methanolic
solutions, in which product selectivity was greatly dependent on
water content [21]. It should be noted that actual lignin and bio-
oils always contain plenty of water. Therefore, the development of
highly efficient and water-tolerant catalyst system is desirable for
also beneficial. Pt/C [27] and Ni-Re/ZrO [28] were evaluated in the
2
HDO of phenols into aromatic hydrocarbons in water. However,
the yields and selectivities of aromatic products are still insuffi-
cient. We previously reported the aqueous-phase conversion of
phenols into aliphatic hydrocarbons by Pt/AC (activated carbon)
[29,30]. During our continuous efforts to improve the catalyst effi-
ciency, we found that Pt-Re/ZrO2 catalysts facilitated the HDO of
4-propylphenol (1) into n-propylbenzene (2) with high yields and
selectivities (Scheme 1). Herein, we report the details of character-
ization and catalytic behavior of Pt-Re/ZrO2 in the aqueous-phase
HDO reaction.
2. Experimental
2.1. General
ZrO2 (JRC-ZRO-2), TiO2 (JRC-TIO-4(2)) and CeO2 (JRC-CEO-
∗ Corresponding author. Tel.: +81 11 706 9140; fax: +81 11 706 9139.
E-mail address: fukuoka@cat.hokudai.ac.jp (A. Fukuoka).
2) were supplied by Catalysis Society of Japan. ␥-Al O3 (A-11)
was purchased from Nishio Industry and SiO2 (CAB-O-SIL M-5)
2
http://dx.doi.org/10.1016/j.cattod.2014.01.022
0
920-5861/© 2014 Elsevier B.V. All rights reserved.
Please cite this article in press as: H. Ohta, et al., Selective hydrodeoxygenation of lignin-related 4-propylphenol into n-propylbenzene
in water by Pt-Re/ZrO2 catalysts, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.01.022

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Table 1
Structural parameters of catalysts.
SBET (m2
g
−1
)a
dp (nm)b
dTEM (nm)c
Catalyst
ZrO2
Pt/ZrO2
Pt-Re/ZrO2
Pt-Re/ZrO2 after the reaction
90
72
74
65
3.3
3.7
3.3
3.7
−
f
−
d
f
−
e
1.7 ± 0.2
a
BET surface area.
Average pore diameter.
Mean diameter of Pt particle by TEM analysis.
Pt/Re molar ratio 3.
After the reaction in entry 18, Table 3.
Pt nanoparticles were not observed.
b
c
d
e
f
Scheme 1. Selective conversion of 4-propylphenol 1 to n-propylbenzene 2.
from Acros Organics. These metal-oxide supports were calcined
◦
in air at 400 C for 4 h before use. Activated carbon (activated
◦
◦
2
00 C for 100 min, followed by cooling to 50 C under He flow. The
charcoal Norit SX Ultra, denoted as AC) was purchased from
Aldrich and used without further treatment. The following chem-
◦
chemisorption of CO was performed at 50 C (with 10% CO in He),
where an equilibrium was assumed when no further CO adsorption
was observed.
icals were purchased and used as received: H PtCl ·6H O and
2
6
2
HAuCl ·4H O from Kanto; NH ReO , SnCl ·2H O, Fe(NO ) ·9H O,
4
2
4
4
2
2
3
3
2
PdCl , Na WO ·2H O, (NH ) Mo7O ·4H O and Bi(NO ) ·5H O
2
2
4
2
4
6
24
2
3
3
2
2
.4. Catalytic HDO of 4-propylphenol in water
from Wako; Ga(NO ) ·nH O and In(NO ) ·3H O from Junsei; aque-
3
3
2
3
3
2
ous solution of H IrCl from Furuya Metals; 4-propylphenol,
2
6
A typical procedure: 4-propylphenol (5.0 mmol, 681 mg), cata-
propylbenzene, propylcyclohexane, 4-propylcyclohexanol and 4-
propylcyclohexanone from Tokyo Chemical Industry.
lyst (2 wt% Pt loading, 98 mg) and water (40 mL) were charged in
a well dried high-pressure batch reactor (OM Lab-Tech MMJ-100,
SUS316, 100 mL). After pressurization with H2 to 2 MPa at room
temperature, the reactor was heated to the desired reaction tem-
perature with continuous stirring at 600 rpm. Then, the reactor was
kept at the reaction temperature for 1 h. After cooling to room tem-
perature, the reaction mixture was extracted with ethyl acetate
and the organic layer was analyzed by GC and GC–MS using 2-
isopropylphenol as an internal standard. GC analyses were carried
out using a Shimadzu GC-14B equipped with an integrator (C-R8A)
with a capillary column (HR-1, 0.25 mm i.d. × 50 m). GC–MS anal-
yses were measured by a Shimadzu GC-2010/PARVUM2 equipped
with the same column. The catalyst was recovered by centrifuga-
tion, followed by washing with ethyl acetate and dried in an oven
at 120 C for 2 h. The recovered catalyst was reused in the next
reaction.
For the time-course study, many batch reactions at different
time were performed separately. Here, the reaction time “0” was
defined as the time when the temperature of the reaction mixture
just reached the reaction temperature.
2
.2. Preparation of catalysts
All the catalysts were prepared by the co-impregnation method
and Pt loading was kept at 2 wt%. For example, the procedure for
preparing Pt-Re/ZrO (Pt/Re molar ratio 3) was as follows: aqueous
2
solutions of H PtCl (0.211 mmol in 10 mL water) and NH ReO
2
6
4
4
(
0.070 mmol in 300 ␮L water) were sequentially added to a mix-
ture of ZrO (2.00 g) and water (30 mL) with continuous stirring. The
reaction mixture was stirred at room temperature for 15 h, evapo-
rated to dryness and dried under vacuum. The sample was calcined
in a fixed-bed flow reactor with O2 (30 mL min ) at 400 C for 2 h,
then reduced with H2 (30 mL min ) at 400 C for 2 h to give Pt-
Re/ZrO2 catalyst. For Pt-Re/AC, only H2 reduction was performed
after drying the impregnated sample. The prepared catalysts were
then exposed to air at room temperature for their passivation.
2
−1
◦
−1
◦
◦
2
.3. Catalyst characterization
Powder X-ray diffraction (XRD) patterns were recorded on a
Rigaku MiniFlex using Cu K␣ radiation (ꢀ = 0.15418 nm) at 30 kV
3. Results and discussion
and 15 mV. N adsorption–desorption analyses were performed
2
◦
at −196 C with a BEL Japan BELSORP-mini II after heating the
3.1. Characterization of Pt/ZrO2 and Pt-Re/ZrO2 catalysts
Characterization of ZrO , Pt/ZrO , and Pt-Re/ZrO were per-
◦
samples at 120 C under vacuum for 2 h. Specific surface areas of
samples were calculated according to the Brunauer–Emmett–Teller
2
2
2
(
BET) method. Pore size distributions were estimated by the
formed by N2 adsorption and XRD analyses. The structural
parameters were summarized in Table 1. ZrO , Pt/ZrO , and Pt-
Barrett–Joyner–Halenda (BJH) method. X-ray photoelectron spec-
troscopy (XPS) was performed with a JEOL JPC-9010MC using Mg
K␣ radiation (1253.6 eV) at 100 W and a pass energy of 20 eV. The
binding energies were calibrated using adventitious carbon (C1s
peak at 284.8 eV). Pt L - and Re L -edge X-ray absorption fine struc-
ture (XAFS) was measured at room temperature in the transmission
mode with a synchrotron radiation (ring energy 2.5 GeV, 450 mA)
through a Si(1 1 1) double-crystal monochromator at BL-12 C beam
line on KEK-PF (Proposal No. 2013G222). The measurement was
conducted in the quick XAFS mode (20 s for 1 scan) and repeated
2
−1
2
2
Re/ZrO2 have BET surface areas of 72−90 m g with a pore size
of 3.3−3.7 nm. In the XRD patterns of these samples, large peaks
of monoclinic ZrO2 phase and a small peak of tetragonal ZrO2
phase were observed (Fig. 1(a)–(c)). TEM and XPS measurements
of Pt/ZrO2 and Pt-Re/ZrO2 were conducted to estimate the metal
particle size and the electronic states of the Pt and Re species. The
Pt nanoparticles were not observed on the TEM images of Pt/ZrO2
3
3
and Pt-Re/ZrO , suggesting the high dispersion of Pt nanoparti-
2
cles (Fig. 2(a) and (b)). The XPS analyses of Pt/ZrO2 and Pt-Re/ZrO2
showed that Pt existed as Pt(0) and oxidized Pt species on the
catalyst surface (Fig. 3). The peaks in Pt4f region of Pt-Re/ZrO2
(Pt4f7/2 = 72.7 eV) were observed at higher binding energy than that
of Pt/ZrO2 (Pt4f7/2 = 71.7 eV), suggesting the interaction of Pt with
Re [31,32]. The Re4f peaks of Pt-Re/ZrO2 indicate that the major Re
species is Re(6+); however, more information was not obtained due
6
4 times to improve the signal–noise ratio. Transmission elec-
tron microscopy (TEM) was conducted with a JEOL JEM-2000ES at
an accelerating voltage of 200 kV. Energy dispersive X-ray spec-
troscopy (EDX) was measured on a Shimadzu Rayny EDX-720. CO
chemisorption was carried out with a BEL Japan BELCAT-A. Prior
to the chemisorption experiment, a sample was reduced by H2 at
Please cite this article in press as: H. Ohta, et al., Selective hydrodeoxygenation of lignin-related 4-propylphenol into n-propylbenzene
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the remaining part was metal in the catalyst, using the spectra of Pt
foil and PtO2 [33]. As to Re L -edge, intensity of the white line for
3
Pt-Re/ZrO2 corresponded to those for tetra- to hexa-valent oxides
[
34,35]. These oxide species could be formed by the passivation
in the catalyst preparation, due to high dispersion of metals. It is
known that Ru, also a precious metal, particles less than 2 nm is
converted to RuO ·2H O in air even at room temperature [36]. Note
2
2
that these oxides can be reduced under reaction conditions in the
presence of H2 to work as catalysts [37].
3.2. HDO of 4-propylphenol by supported Pt catalysts
Fig. 1. XRD patterns of (a) ZrO2; (b) Pt/ZrO2; (c) Pt-Re/ZrO2; (d) Pt-Re/ZrO2 after the
reaction (Table 3, entry 18). Circles (᭹): monoclinic ZrO2. Diamond (♦): tetragonal
ZrO2.
HDO of 4-propylphenol (1) was examined with various Pt cat-
◦
alysts supported on ZrO2 in water at 300 C for 1 h under 2 MPa
H2 (Table 2). Monometallic Pt/ZrO2 gave propylbenzene (2) in 40%
yield (65% selectivity) with aliphatic hydrocarbons (3 + 4; 15% selec-
tivity) and oxygenates (5 + 6; 16% selectivity) (entry 1). The use of
bimetallic catalysts greatly affected the product distribution. Pt-
to the overlapping of the peaks of Re4f and Zr4s as well as the low
Re loading (0.67 wt%).
XAFS spectra were measured to elucidate the oxidation states of
Re/ZrO converted 1 into 2 in 57% yield with 85% selectivity, where
2
Pt and Re species on Pt-Re/ZrO2 (Fig. 4). With regard to Pt L -edge
5 and 6 were formed in only 1% selectivity (entry 2). The addition
of Sn, Ir, Ga, and Fe had little effect on the catalytic performance
of Pt/ZrO2 (entries 3−6). Au, Pd, W and In gave higher yields of
3−6, leading to a decrease in the selectivity of 2 (entries 7−10). By
contrast, Pt-Mo/ZrO2 and Pt-Bi/ZrO2 showed much lower activity
3
X-ray near edge structure (XANES), Pt-Re/ZrO2 provided a larger
white line than that of Pt foil at 11565 eV. This result also shows
that Pt is partially oxidized as indicated by the XPS study. A curve
fitting suggested that ca. 25% fraction of Pt species was oxides and
Fig. 2. TEM images of (a) Pt/ZrO2; (b) Pt-Re/ZrO2; (c) Pt-Re/ZrO2 after the reaction (Table 3, entry 18).
Fig. 3. XPS spectra for the Pt4f and Re4f regions of (a) Pt/ZrO2; (b) Pt-Re/ZrO2; (c) Pt-Re/ZrO2 after the reaction (Table 3, entry 18).
Fig. 4. Pt L3-edge and Re L3-edge XANES spectra of Pt-Re/ZrO2 catalysts.
Please cite this article in press as: H. Ohta, et al., Selective hydrodeoxygenation of lignin-related 4-propylphenol into n-propylbenzene
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Table 2
a
Aqueous-phase HDO of 4-propylphenol 1 by supported Pt catalysts .
.
Entry
Catalyst
Conversion (%)
Yield (selectivity)b (%)
2
3
4
5
6
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
Pt/ZrO2
62
67
61
65
58
54
63
59
66
51
8.8
4.4
58
41
45
8.1
90
40 (65)
8 (13)
9 (13)
10 (16)
9 (14)
8 (14)
7 (13)
11 (17)
9 (15)
7 (11)
1 (2)
8 (13)
1 (1)
3 (5)
4 (6)
2 (3)
4 (7)
4 (6)
14 (24)
5 (8)
6 (12)
0.9 (10)
0.6 (14)
1 (2)
2 (3)
0.2 (0.3)
0
Pt-Re/ZrO2
Pt-Sn/ZrO2
Pt-Ir/ZrO2
Pt-Ga/ZrO2
Pt-Fe/ZrO2
Pt-Au/ZrO2
Pt-Pd/ZrO2
Pt-W/ZrO2
Pt-In/ZrO2
Pt-Mo/ZrO2
Pt-Bi/ZrO2
Pt-Re/TiO2
Pt-Re/Al2O3
Pt-Re/CeO2
Pt-Re/SiO2
Pt-Re/AC
57 (85)
44 (72)
43 (66)
39 (67)
34 (63)
37 (59)
33 (56)
33 (50)
24 (47)
4.9 (56)
2.2 (50)
41 (71)
27 (66)
24 (53)
1.3 (16)
3 (3)
0.1 (0.1)
0.1 (0.2)
2 (3)
2 (3)
3 (5)
2 (4)
5 (8)
1 (2)
14 (21)
1 (2)
1.8 (21)
1.0 (23)
1 (2)
1 (3)
0
1 (2)
1 (2)
2 (3)
2 (3)
2 (3)
2 (4)
0.3 (3)
0.2 (5)
0.3 (1)
1 (2)
1
1
1
1
1
1
1
1
9 (18)
0.9 (10)
0.4 (9)
13 (22)
4 (10)
11 (24)
0.4 (5)
17 (19)
4 (10)
4 (9)
1.8 (22)
62 (69)
2 (4)
0.1 (1)
0
3.7 (46)
0
a
◦
Reaction conditions: 4-propylphenol 1 (5.0 mmol, 681 mg), catalyst (98 mg, 2 wt% Pt loading, Pt/M molar ratio 3), water (40 mL), initial H2 pressure at RT = 2 MPa, 300 C,
1
h, 600 rpm.
b
Selectivity is based on the substrate conversion.
(
1
4−9% conversion) and selectivity of 2 (50−56%) (entries 11 and
2). Catalyst supports have a significant influence on the catalytic
activity in this reaction. Pt-Re catalysts supported on TiO , Al O ,
Reaction temperature had significant effect on the selectivity of
the products (Fig. 6). The reaction was completed at 260 C to give
◦
2 and 3 in 60% and 39% yields, respectively. The selectivity of 2 was
increased at higher temperatures, and the highest yield of 2 was
2
2
3
and CeO2 were moderately active for the reaction, affording lower
◦
yields of 2 than Pt-Re/ZrO2 (entries 13−15). In sharp contrast, Pt-
obtained at 280 C (73% yield, 81% selectivity). Decrease in the con-
◦
Re/SiO was less active with only 8% conversion, giving oxygenates
version of 1 at 300 C may be attributed to the dehydrogenation of
2
5
and 6 as major products (entry 16). In addition, Pt-Re/AC greatly
facilitated the conversion of 1 into 3 (17% yield) and 5 (62% yield)
entry 17). Among the catalysts tested, Pt-Re/ZrO2 was found to be
initially formed 5 into 1 (vide infra).
The recyclability of Pt-Re/ZrO2 was evaluated in the HDO of
◦
(
1 at 280 C (Table 3). After the 1st run (entry 18), the catalyst
the most effective catalyst in the selective HDO of 1 into 2 in water.
To further optimize the reaction conditions, Pt/Re molar ratio
and reaction temperature were investigated. Fig. 5 shows the influ-
ence of different Pt/Re ratio on the catalytic performance. The
conversions were nearly identical in the Pt/Re ratios of 1−4, but
the yield and selectivity of 2 were affected by the Pt/Re ratio. The
Pt/Re ratio of 3 was the best composition for the production of 2.
was recovered by centrifugation and successively subjected to
the next reaction. However, the catalytic activity was dramati-
cally reduced to give trace amounts of products (entry 19). Pt/ZrO2
and Pt-Re/TiO , which showed good catalytic activity in Table 2,
2
were also employed in the reuse experiments; however, the cat-
alytic activities were completely lost in the 2nd runs (entries
21−24). To find out the cause of catalyst deactivation, the recovered
Fig. 5. Influence of Pt to Re molar ratio on the HDO of 4-propylphenol 1. Reaction
Fig. 6. HDO of 4-propylphenol 1 by Pt-Re/ZrO2 at different reaction temperatures.
conditions: see entry 2 in Table 2.
Reaction conditions: see entry 2 in Table 2.
Please cite this article in press as: H. Ohta, et al., Selective hydrodeoxygenation of lignin-related 4-propylphenol into n-propylbenzene
in water by Pt-Re/ZrO2 catalysts, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.01.022

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Table 4
5
Table 3
Reuse experiments of Pt-Re/ZrO2 in the HDO of 4-propylphenol 1.a
Control experiments with Pt-Re/ZrO2 catalyst .
a
Entry
Run
Conversion (%)
Yield (%)
Entry
Substrate
Conversion (%)
Yield (%)
2
3
4
5
6
1
2
3
4
5
6
18
19
20
21
22
23
24
25
26
1st
91
1.4
1.6
71
2.5
71
0.1
100
100
73
0.3
0.2
47
0
44
0
0
13
0
0
13
0
17
0
0.1
0
0
2
0
0
0
0
0
3
1
27
28
29
2
3
5
12
2.8
98
0
0
4
−
12
−
0
0.3
0
0
0
−
0
0
0
2nd
2nd
1st
2nd
1st
2nd
1st
2nd
0.8
0.8
3
0.2
10
0.1
0
0
0.3
0.6
4
0
0
0
0
0
2.3
72
b
c
19
a
Reaction conditions: substrate (5.0 mmol), Pt-Re/ZrO2 (98 mg, 2 wt% Pt loading,
c
◦
Pt/Re molar ratio 3), water (40 mL), initial H2 pressure at RT = 2 MPa, 300 C, 1 h,
00 rpm.
d
d
e
e
6
>99
84
0
to the coke formation or the oxidation of Pt(0) species. A control
experiment was carried out: Pt-Re/ZrO was pretreated at the reac-
a
Reaction conditions: 4-propylphenol 1 (5.0 mmol, 681 mg), Pt-Re/ZrO2 (98 mg,
2
2
wt% Pt loading, Pt/Re molar ratio 3), water (40 mL), initial H2 pressure at RT = 2 MPa,
2
◦
tion conditions (2 MPa H , 280 C, H O, 1 h) without 1, then it was
2 2
◦
80 C, 1 h, 600 rpm.
b
Regenerated catalyst after the 1st run (entry 18) was used. Regeneration condi-
used for the HDO of 1. As a result, the catalyst was also deactivated
1% conversion), indicating that the catalyst was not stable under
◦
◦
tions: O2 calcination at 400 C for 2 h, then H2 reduction at 400 C for 2 h.
(
c
Pt/ZrO2 catalyst was used.
Pt-Re/TiO2 catalyst was used.
Without water.
the reaction conditions. Besides, when the reaction was performed
without water solvent, 3 was obtained as a sole product and the
catalyst was reusable in the 2nd run with slight loss of activity
d
e
(entries 25 and 26). These results suggest that high-temperature
Pt-Re/ZrO2 catalyst after the 1st run was analyzed by EDX, XRD,
XPS, XAFS, TEM and adsorption of N2 and CO. First, no leaching of
Pt was observed by EDX analysis. The BET surface areas and pore
sizes were slightly changed before and after the reaction (Table 1).
The XRD pattern of the recovered catalyst showed the disappear-
ance of the peak of tetragonal ZrO2 phase observed in the fresh
catalysts, suggesting the structural change of ZrO2 support during
the reaction (Fig. 1(d)). The XPS spectrum of spent Pt-Re/ZrO2 is
typically shown in Fig. 3(c). In the XPS study, clear decrease of the
peak intensities in Pt4f, Zr3d and Re4f regions and increase in C1s
region were observed. It implies that coke is formed on the catalyst
surface. The Pt4f peaks showed that the surface Pt(0) was oxidized.
On the other hand, the Re4f peak suggests that Re(6+) still exists
as a major Re species. Pt L3- and Re L3-edge XAFS measurements
provided similar spectra for fresh and spent Pt-Re/ZrO2 catalysts,
showing that the bulk phase of Pt nanoparticles was not affected
under the reaction conditions (Fig. 4). The TEM analyses of spent
Pt-Re/ZrO2 showed the sintering of the Pt nanoparticles, but the Pt
particle size was still small (1.7 nm) (Table 1; Fig. 2(c)). In contrast
to the result of TEM analysis, CO chemisorption of spent Pt-Re/ZrO2
provided larger Pt particle size of 8.0 nm. This underestimation of
Pt dispersion might be due to the coke formation. These results sug-
gest that the deactivation of Pt-Re/ZrO2 might be due to the coke
formation, the oxidation of Pt(0), or sintering of Pt. To check the
first two possibilities, the recovered catalyst after the 1st run was
water plays a key role in the deactivation. The Pt sintering would
not be the main cause of deactivation because the Pt particle size is
still small (<2 nm). Perhaps, the catalyst deactivation is due to the
water-induced wrapping of Pt nanoparticles by ZrO2 like the SMSI
phenomenon [38].
◦
The time-course of the HDO of 1 at 300 C was shown in Fig. 7.
As shown in Fig. 7(a), Pt-Re/ZrO2 gave 85% conversion even at 0 h,
affording 2 (51% yield), 3 (11%), 4 (0.2%), 5 (21%) and 6 (0.4%). Inter-
estingly, the conversion of 1 and the amount of 5 decreased with
reaction time, suggesting the dehydrogenation of 5 into 1. The yield
of 2 also increased by time, and the highest yield was obtained
after 1 h (57%, entry 2 in Table 2). In contrast, the amount of 3 was
kept constant during the reaction. It is suggested that 3 was formed
◦
during the temperature rise from room temperature to 300 C. The
HDO by Pt/ZrO showed a similar time-course, but the yield of 2 did
2
not changed during the reaction probably due to the catalyst deac-
tivation (Fig. 7(b)). These results indicated that the addition of Re
improved the durability of Pt/ZrO catalyst. Probably, the Re species
2
prevent the Pt sintering during the reaction, which is consistent
with the results of TEM analysis of spent Pt-Re/ZrO2 (Table 1).
To gain further insight into the reaction pathways from 1 to 2,
control experiments were carried out with Pt-Re/ZrO2 catalyst at
◦
300 C (Table 4). The reaction of 2 afforded 3 in 12% yield via the
hydrogenation of aromatic ring (entry 27). 3 was converted only
in 3%, giving small amounts of 2 and 4 (entry 28). It is clearly indi-
cated that the dehydrogenation of 3 into 2 was a minor pathway
in the HDO of 1. As shown in entry 29, Pt-Re/ZrO2 greatly pro-
moted the reaction of 5 to give 1 (4%), 2 (72%) and 3 (19%). There
◦
regenerated at 400 C using O2 followed by H2 reduction and then
used in the next run. However, the reaction gave almost no prod-
ucts (entry 20). It is indicated that the deactivation is not attributed
◦
Fig. 7. Time-course of the HDO of 4-propylphenol 1 at 300 C by (a) Pt-Re/ZrO2 and (b) Pt/ZrO2. Reaction conditions: see entries 1 and 2 in Table 2.
Please cite this article in press as: H. Ohta, et al., Selective hydrodeoxygenation of lignin-related 4-propylphenol into n-propylbenzene
in water by Pt-Re/ZrO2 catalysts, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.01.022

G Model
CATTOD-8869; No. of Pages6
ARTICLE IN PRESS
H. Ohta et al. / Catalysis Today xxx (2014) xxx–xxx
Acknowledgements
6
This work was supported by a Grant-in-Aid for Scientific
Research (KAKENHI, 24760633) from the Japan Society for the Pro-
motion of Science (JSPS). We would like to thank Mr. O. Kawabata
for the analysis of XAFS spectra.
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Please cite this article in press as: H. Ohta, et al., Selective hydrodeoxygenation of lignin-related 4-propylphenol into n-propylbenzene
in water by Pt-Re/ZrO2 catalysts, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.01.022