Rhenium-promoted Pt/WO3/ZrO2: An efficient catalyst for aqueous glycerol hydrogenolysis under reduced H2 pressure

Article abstract of DOI:10.1039/c6ra21198d

Rhenium, the non-noble metal with an acceptable price, was found to be a good additive that largely improved Pt/WO₃/ZrO₂ catalysis for glycerol hydrogenolysis. Compared with conventionally employed Pt/WO₃/ZrO₂, the Re-promoted catalyst led to almost quantitative glycerol conversion (>99% vs. 57.7%), giving useful C3 alcohols in excellent total selectivity (>95%) under reduced reaction pressure (2.5 MPa). The addition of Re led to such an impressive enhancement of the catalyst activity that even the reaction performed under atmospheric H₂ pressure (0.1 MPa) afforded 96.8% glycerol conversion and a good selectivity of C3 compounds at 95.2%. Further XRD, Raman, BET, CO chemisorption, TEM, H₂-TPR, XPS, NH₃-TPD, ¹H MAS NMR and Py-IR studies indicated that introduction of Re greatly improved the dispersion of Pt and catalyst acidity, and resulted in this largely enhanced catalyst activity.

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Rhenium-promoted Pt/WO3/ZrO2: An efficient catalyst for
aqueous glycerol hydrogenolysis under reduced H2 pressure
Qing Tong,a,b Anyi Zong,a,b Wei Gong,c Lei Yu,*d and Yining Fan*a
Received 00th January 20xx,
Accepted 00th January 20xx
Rhenium, the non-noble metal with acceptable price, was found to be a good additive that largely improved Pt/WO3/ZrO2
catalyst for glycerol hydrogenolysis. Compared with conventionally employed Pt/WO3/ZrO2, the Re-promoted catalyst led
to almost quantitative glycerol conversion (>99% vs. 57.7%), giving useful C3 alcohols in excellent total selectivity (> 95%)
under reduced reaction pressure (2.5 MPa). The addition of Re led to so impressive enhancement of the catalyst activity
that even the reaction performed under atmosphere H2 pressure (0.1 MPa) afforded 96.8% glycerol conversion and good
selectivity of C3 compounds at 95.2%. Further XRD, Raman, BET, CO chemisorption, TEM, H2–TPR, XPS, NH3–TPD, 1H MAS
NMR and Py-IR studies indicated that introduction of Re greatly improved the dispersion of Pt and catalyst acidity, and
resulted in this largely enhanced catalyst activity.
DOI: 10.1039/x0xx00000x
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explosive H2 in organic synthesis.13 The procedure may also
o
Introduction
provide acetol (b.p. 145ꢀ146 C) as the byꢀproduct, which is an
intermediate to produce polyols and acrolein, spices in food
Glycerol is an abundantly generated byꢀproduct during the
biodiesel production process. Currently, about 1 kg of crude
glycerol is generated for every 9 kg of biodiesel production.
With the increase of demand for biodiesel, glycerol will be over
supplied in market.1 Thus, chemists have paid much attention to
the conversion of glycerol into highꢀvalued downstream
chemicals through hydrogenolysis, dehydration, reforming,
etherification et. al.2ꢀ9 Wherein, hydrogenolysis of glycerol is a
very important industrial process because it transforms the
abundant biomass into C3 alcohols such as 1,3ꢀpropanediol
(1,3ꢀPDO), 1, 2ꢀpropanediol (1,2ꢀPDO), 1ꢀpropanol (1ꢀPO) and
2ꢀpropanol (2ꢀPO), which are all useful chemicals in industrial
production: 1,3ꢀPDO (b.p. 210ꢀ211 oC) is an important raw
material in the synthesis of polytrimethylene terephthalate
(PTT);10 1,2ꢀPDO (b.p. 188.2 oC) is widely employed as the
raw material to produce unsaturated polyester, wetting agent in
cosmetics, toothpaste and perfumed soap, antifreeze and et.
al;11 1ꢀPO (b.p. 97.1 oC) is an important solvent or starting
material in pesticide, medicine and perfume industries and its
market demand is growing fast in recent years;12 2ꢀPO (b.p.
82.5 oC) is an excellent organic raw material and industrial
solvent in medicine, ink, cosmetics and coating industries and it
is also employed as a safe hydrogen source instead of the
chemistry and skin tanning agents in cosmetic industry.14 The
above C3 compounds can be separated by rectification in largeꢀ
scale preparation.
Currently, glycerol hydrogenolysis was performed using
transition metal catalysts such as Pt,3ꢀ4 Rh,5 Ir,6 Cu,7 Ni8 and
Ru.9 Among reported works, Pt/WO3/ZrO2 attracted much
attention owing to its strong acidity and high thermal and
chemical stability,15 and has been widely employed in glycerol
hydrogenolysis.3aꢀc In 2008, Sasaki et al. first obtained a 64.2%
selectivity of C3 alcohols with 78.4% glycerol conversion in
DMI solvent using Pt/WO3/ZrO2 catalyst at 170 oC and under 8
MPa pressure in batch reactor for the first time (Table 1, entry
1).3a Latter, Chen et al. achieved an improved 70.1% selectivity
of C3 alcohols with 70.2% glycerol conversion in aqueous
phase using Pt/WO3/ZrO2 catalyst at 130 oC and 4 MPa in
fixedꢀbed reactor (Table 1, entry 2).3b Zhu et al.3c developed the
nice SiO2ꢀmodified Pt/WO3/ZrO2 catalyst for glycerol
hydrogenolysis, which has enhanced Pt dispersion and catalyst
acidity, and led to the excellent 97.6% selectivity of C3
alcohols with 40.1% glycerol conversion at 180 oC and under 5
MPa pressure in fixedꢀbed reactor (Table 1, entry 3). But in the
above reported works, the glycerol conversions were low,
resulting in the low production capacity from the industrial
viewpoint. Thus, improvement of the catalyst to enhance
glycerol conversion is urgently required.
a.Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Key Laboratory of
Vehicle Emissions Control, Jiangsu Provincial Key Laboratory of
Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing
University, Nanjing 210093, China. Email: ynfan@nju.edu.cn; Fax: +86ꢀ25ꢀ
83317761; Tel: +86ꢀ25ꢀ83594620.
On the other hand, rhenium is a nonꢀnoble transition metal
with acceptable price for industrial production and its oxide is
an acidic material which is usually used to improve catalyst
properties in aqueous phase reforming, hydrogenolysis,
hydrodeoxygenation et. al.16 Our groups aimed to develop
green techniques with industrial potential.17 Recently, we
b.Nanjing UniversityꢀYangzhou Chemistry and Chemical Engineering Institute,
Yangzhou, 211400, China.
c. Jinling College, Nanjing University, Nanjing 210089, China.
d.School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou,
225002, China. Email: yulei@yzu.edu.cn.
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Figure
catalyst; (
1
b
Catalytic performances of:
(a) 2Pt/WO3/ZrO2
successfully employed rhenium oxide as an additive to improve
the Pt/WO3/ZrO2 catalyst for glycerol hydrogenolysis. It was
found that PtꢀRe/WO3/ZrO2 catalysts had very good catalytic
activity and the glycerol conversion was enhanced to the almost
quantitative yield while the total selectivity of C3 alcohols was
kept at >95% level in aqueous solution (Table 1, entry 4).
Moreover, the reaction pressure was reduced to 2.5 MPa, which
largely facilitated further industrial applications. The catalyst
was so active that even the reaction performed under
atmosphere H2 pressure afforded excellent glycerol conversion
(96.8%) and good C3 compound selectivity (95.2 %). Herein,
we wish to report our findings.
) 1.5Ptꢀ0.8Re/WO3/ZrO2 catalyst.19
A
series of 2PtꢀxRe/WO3/ZrO2 catalysts were then
evaluated. The reactions finished within 18 h and extended
reaction times did not have any effects on neither glycerol
conversion nor product selectivity, as shown in Figure S1 in
ESI. With the promotion of Re content, glycerol conversion
increased considerably to near 100% (Figure 2A, curves
). However, excessive Re led to decreased glycerol conversion
on the contrary (Figure 2A, curves ) mainly due to the
bꢀd vs.
a
eꢀf
coverage of active Pt sites by Re according to the CO
adsorption data (Table 2, vide infra). Without Pt,
2Re/WO3/ZrO2 exhibited very poor activity (Figure 2A, curve
Table 1 Comparison of the methodologies
g
), showing that Re had little catalytic activity in glycerol
hydrogenolysis. Figures 2B and 3 indicated that the addition of
Re did not restrain the total selectivity of C3 alcohols. Finally,
2Ptꢀ0.1Re/WO3/ZrO2 and 2Ptꢀ0.8Re/WO3/ZrO2 were screened
out to be the best two catalysts: The former employed very low
rhenium oxide additives, but led to the highest glycerol
conversion at 99.9% and excellent C3 alcohol selectivity at
95.7%; The latter resulted in slightly decreased glycerol
conversion (99.0%) and C3 alcohol selectivity (95.6%), but
compared with 2Ptꢀ0.1Re/WO3/ZrO2, the selectivity of the
important chemical 1, 3ꢀPDO was obviously enhanced (20.4%
vs. 16.5%).19
P
Entry Catalyst
C
S
Ref.
(MPa)a
(%)b
(%)c
1
2
Pt/WO3/ZrO2
8
4
78.4
70.2
64.2
70.1
3a
3b
Pt/WO3/ZrO2
3
4
Pt/WO3/ZrO2/SiO2
5
40.1
97.6
3c
Pt-Re/WO3/ZrO2 2.5
>99
>95
This
work
a Reaction pressure; b Glycerol conversions; c Total selectivity of C3 alcohols
(1,3ꢀPDO, 1,2ꢀPDO, 1ꢀPO and 2ꢀPO).
Results and discussion
We initially prepared the 1.5Ptꢀ0.8Re/WO3/ZrO2 catalyst18
through sequential wetness impregnation method (see
experimental section, vide infra) and compared its catalytic
activity with the conventionally employed 2Pt/WO3/ZrO2
catalyst in glycerol hydrogenolysis at 175 oC, 2.5 MPa. As
shown in Figure 1, 2Pt/WO3/ZrO2 led to moderate glycerol
conversion at 57.7%. After introducing ReOx as additive, the
glycerol conversion was enhanced to 68.2% with C3 alcohol
selectivity at >90%. Further investigations disclosed that using
2Ptꢀ0.8Re/WO3/ZrO2 as catalyst largely enhanced the glycerol
conversion to 99.0% and led to 95.6% C3 alcohol selectivity.19
Figure
catalysts at 175 C, 2.5 MPa: (A) Glycerol conversion; (B) C3
alcohol selectivity; ( ) x = 0, ( ) x = 0.1, ( ) x = 0.36, ( ) x =
0.8, ( ) x = 1, ( ) x = 2, (
) 2Re/WO3/ZrO2.19
2 Catalytic performances of 2PtꢀxRe/WO3/ZrO2
o
a
b
c
d
e
f
g
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o
o
o
(B) C3 alcohol selectivity; (
) 170 oC, ( ) 175 oC.19
a) 135 C, (b) 155 C, (c) 165 C,
(
d
e
A series of reactions performed under different H2 pressure
were tested. As shown in Figures 5, reactions performed at
reduced H2 pressure did not enhance glycerol conversion, but
led to the generation of acetol with the H2 pressure less than 2.0
MPa.19 It was notable that even the reaction performed at
atmosphere H2 pressure could led to excellent glycerol
conversion (Figure 5, curve a) and very high selectivity of C3
compounds, in which the useful fine chemical acetol was
generated in 63.1% selectivity.19 Although acetol was
considered not to be the hydrogenation product, H2 was still
necessary for the reaction. Contrast experiments performed
under N2 atmosphere led to very low glycerol conversion
(<30%), while the C3 compound selectivities remained at high
level (Figure 6).19
Figure
3 Catalytic performances of 2PtꢀxRe/WO3/ZrO2
catalysts with different Re content after 12 h reaction (other byꢀ
products: acetone, propionate acid and ethylene glycol).
Using 2Ptꢀ0.8Re/WO3/ZrO2 as catalyst, a series of reactions
at different temperatures were then tested. Obviously, high
temperature was an essential factor for the reaction (Figure 4A).
o
Reaction performed at 135 C afforded no more than 10 % of
o
glycerol conversion. Reactions at 155ꢀ170 C led to ca 30.5ꢀ
o
56.2 % glycerol conversions. It was finally found that 175 C
was the best reaction temperature, giving the excellent >90 %
glycerol conversions. Figure 4B showed that the reactions at
o
135ꢀ175 C led to similar C3 alcohol selectivities at ca 92.9ꢀ
97.3 %.19
Figure 5 Catalytic performances of 2Ptꢀ0.8Re/WO3/ZrO2 under
different H2 pressure boost: (A) Glycerol conversion; (B) C3
compound selectivity; (
0.5 MPa, ( ) 1.0 MPa, (
a
) atmospheric pressure (0.1 MPa), (
b)
c
d
) 1.5 MPa, ( ) 2.0 MPa, (
e
f
) 2.5 MPa.19
Figure
4 Catalytic performances of 2Ptꢀ0.8Re/WO3/ZrO2
catalysts under different temperatures: (A) Glycerol conversion;
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did not obviously affected the diffraction peaks of
WO3, Pt and ReOx (Figure 7, curves aꢀf vs c’).
mꢀZrO2,
Figure 6 Catalytic performances of (A) 2Pt/WO3/ZrO2; (B)
2Ptꢀ0.8Re/WO3/ZrO2 catalysts under N2 atmosphere.19
The textural properties of 2PtꢀxRe/WO3/ZrO2 catalysts with
different Re contents were then investigated through nitrogen
physisorption isotherms and COꢀchemisorption. As shown in
Table 2, the addition of Re did not change the surface area of
the catalyst much. In contrary, Re addition largely affected CO
adsorption and 2Ptꢀ0.1Re/WO3/ZrO2 led to the highest CO
adsorption (Table 2, entry 2), which was in consistent with its
highest catalytic activity demonstrated by the highest glycerol
conversion at 99.9%. Since CO adsorption indicates the
dispersion state of Pt,20 it can be concluded that an addition of
adequate amount of Re improves the catalysts by increasing
their Pt dispersion. Catalyst with 0.1ꢀ0.8 % of Re had the
Figure 7 XRD patterns of 2PtꢀxRe/WO3/ZrO2 catalysts: (
ZrO2, ( ) WO3/ZrO2, c’) x = 0, before reduced, ( )ꢀ( ) after
reduced; ( ) x = 0, ( ) x = 0.1, ( ) x = 0.36, ( ) x = 0.8, ( ) x =
1, ( ) x = 2.
a)
b
(
c
f
c
d
e
f
g
h
Raman spectra of catalysts are displayed in Figure 8. All of
the samples showed typical bands for monoclinic ZrO2 at 349,
380, 561 and 617 cm−1, which were in consistent with the XRD
results. The band centered at 963 cm−1 in WO3/ZrO2 sample
highest CO adsorption from 60.2ꢀ50.3 ml
/g Pt, which was in
accordance with their performances in glycerol hydrogenolysis
experiments (Table 2, entries 2ꢀ4 vs. 1, 5ꢀ6). Moreover, without was suggested to be the stretch mode of monoꢀoxo W=O
corresponding to the highly dispersed WOx species.21
Pt, 2Re/WO3/ZrO2 did not have any CO adsorption (Table 2,
Meanwhile, this band shifted gradually from 963 cm−1 to 999
entry 7). Excess Re resulted in decreased CO adsorption due to
cm−1 after Pt and Re loading. The shift might be attributed to
its partial blockage of Pt sites (Table 2, entries 5ꢀ6).4o In
the interaction between metals and external tungsten oxides
which affected the distortion of oxoꢀtungsten species and
addition, TEM images (Figure S2, in ESI) showed that the
addition of Re led to well dispersed Pt particles in 2Ptꢀ
0.8Re/WO3/ZrO2, which was smaller than that in
2Pt/WO3/ZrO2 (ca 2ꢀ3 nm vs. 5ꢀ6 nm), in accordance with the
COꢀchemisorption results.
transferred electrons from the metals to WOx and thus enhanced
the W=O bond strength.4n Besides, a broad band centered at
891 cm−1 was attributed to be the terminal ReO vibrational
mode appeared in 2Ptꢀ0.8Re/WO3/ZrO2.22
Table 2 Physicochemical properties of PtꢀxRe/WO3/ZrO2 catalysts
Entry xRe/wt. % BET (m2/g cat.) CO adsorption (ml/gPt)
1
2
3
0
0.10
0.36
45.6
49.8
49.0
38.4
60.2
56.3
4
5
0.80
1.00
2.00
2.00
49.9
49.5
48.1
50.6
50.3
43.2
22.9
/
6
7a
a Catalyst: Re/WO3/ZrO2
XRD patterns of the catalysts with various Re contents are
given in Figure 7. The diffraction lines at 2θ = 28.3o, 31.5o,
34.3o were attributed to the monoclinic phase of ZrO2 support.3c
On the other hand, no obvious diffraction peaks of WO3, PtOx
and ReOx were observed, reflecting that the metal clusters were
uniformly dispersed onsupport surface.4l Hydrogen reduction
Figure 8 Raman spectra of the catalysts: (
a) ZrO2, (b)
WO3/ZrO2, ( ) 2Pt/WO3/ZrO2, ( ) 2Ptꢀ0.8Re/WO3/ZrO2.
c
d
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Temperatureꢀprogrammed reduction (TPR) was tested to
evaluate the reducibility of catalysts. As shown in Figure 9,
PtOx showed a broad reduction peak at 142 oC in 2Pt/WO3/ZrO2
catalyst. ReOx showed
a
reduction peak at 275oC in
2Re/WO3/ZrO2. The peaks after 350 oC were attributed to WOx
reduction.23 ReOx reduction peaks shifted to low temperature
direction in 2PtꢀxRe/WO3/ZrO2 catalysts, implying that Pt
promoted the reduction of Re precursor in the materials.24
Similarly, the reduction peaks of PtOx transferred to high
temperature along with the increase of Re content and the coꢀ
reduction peak area increased, indicating the enhanced
interaction of the metals with support and better dispersion of
Pt and Re.23b
Figure 10 Pt 4f (A) and Re 4f (B) XPS photo emission peaks of
reduced
(
a
)
2Pt/WO3/ZrO2,
(
b
)
2Ptꢀ2Re/WO3/ZrO2, (c)
2Re/WO3/ZrO2 catalysts.
Since glycerol hydrogenolysis is an acid sensitive reaction
and ReOx is an acidic metal oxide, it is necessary to investigate
acidic properties of the catalysts before and after Re doping.
Figure 11 shows that all of the materials WO3/ZrO2,
2Pt/WO3/ZrO2, 2Ptꢀ0.8Re/WO3/ZrO2 and 2Re/WO3/ZrO2
presented broad TPD profiles, reflecting that the surface acid
strength was widely distributed. The TPD curves of WO3/ZrO2
Figure 9 H2ꢀTPR profiles of 2PtꢀxRe/WO3/ZrO2 catalysts: (
ZrO2, ( ) WO3/ZrO2, ( ) x = 0, ( ) x = 0.1, ( ) x = 0.36, ( ) x =
0.8, ( ) x = 1.0, ( ) x = 1.0, ( ) 2Re/WO3/ZrO2.
a)
b
c
d
e
f
g
h
i
XPS was employed to examine the surface compositions samples could be fitted into peak
Ⅰand peakⅡ, indicating weak
after reduction and the surface chemical states of the catalysts. and medium acid species, respectively. However, peak
Ⅲ
As shown in Figure 10A, 2Pt/WO3/ZrO2 catalyst showed two emerged after Pt and Re loading, which represented the strong
peaks centered at ca. 71.6 and 74.8 eV, which were mainly acid specie.
assigned to be Pt 4f7/2 and Pt 4f5/2 peaks of Pt0, respectively.25a
It is 0.8 eV higher than bulk Pt metal, which might due to
metal–support interaction or a cluster size effect.25b After the
introduction of Re, the two peaks both were shifted to lower
binding energy (4f7/2 = 70.4 eV, 4f5/2 = 74.0 eV). On the other
hand, the peaks in the Re 4f region (Figure 10B) of 2Ptꢀ
2Re/WO3/ZrO2 and 2Re/WO3/ZrO2 catalysts both displayed
three peaks centered at ca. 43.3, 45.5 and 47.9 eV, which were
assigned tobe Re4+, Re6+, and Re7+, respectively.25c It was also
found that the peak area of Re4+ species was significantly
reduced and the ratio of high valence acidic oxides of Re was
enhanced after the addition of Pt to 2Re/WO3/ZrO2 catalyst.
The experimental results indicated that there was electronic
interaction between Pt and Re.
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Figure 11 NH3ꢀTPD profiles of:
(
a
)
WO3/ZrO2,
(b)
increasing of the weak acid, in agreement with H MAS NMR
data.
2Pt/WO3/ZrO2, (
catalysts.
c) 2Ptꢀ0.8Re/WO3/ZrO2, (d) 2Re/WO3/ZrO2
Table 3 The amount of surface acid over catalysts
In 1H MAS NMR profiles, WO3/ZrO2 and 2Pt/WO3/ZrO2
both presented double peaks (Figure 12). Signals at 4.4 ppm
and 4.3 ppm should be ascribed to strong acidic hydroxyl
groups, while the peaks at 0.5 ppm and 0.3 ppm indicated weak
hydroxyl groups.26 However, triple signals emerged in 2Ptꢀ
0.8Re/WO3/ZrO2 spectrum because of the split of the weak
hydroxyl group peak into 1.3 ppm and 0.8 ppm (black
curves).26 In addition, compared with 2Pt/WO3/ZrO2, weak
hydroxyl group signal of 2Ptꢀ0.8Re/WO3/ZrO2 shifted to low
field from 0.3 ppm to 1.3 ppm, indicating that the weak acid
was enhanced by Re loading. It was found that hydrogen
adsorption shifted the strong acidic hydroxyl group signals to
low field and this effect was obviously enhanced after Pt or Re
loading. The phenomena indicated that 2Pt/WO3/ZrO2 and 2Ptꢀ
0.8Re/WO3/ZrO2 are more capable in hydrogen adsorption than
WO3/ZrO2 and the acidity of the strong acidic hydroxyl groups
enhanced after hydrogen adsorption, in consistent with NH3ꢀ
TPD profiles.27 Moreover, the results showed that dissociative
H2 molecules were chemisorbed on Pt sites and led to hydrogen
atoms that could migrate from PtꢀH cluster to the nearby WO3
surface and generated HxWO3, which was called the hydrogen
spill over effect.28
f
entry
cat.a
w.a.b m.ac
s.a.d t.a.e
NH3
1
2
3
4
(I)
463
288
435
368
1080
886
851
636
/
1543
1642
1743
1568
7.45
8.06
8.97
7.54
(II)
(III)
(IV)
468
457
564
a
Catalyst: (I) WO3/ZrO2, (II) 2Pt/WO3/ZrO2, (III) 2Ptꢀ
0.8Re/WO3/ZrO2, (IV) 2Re/WO3/ZrO2; b Weak acid peak area
c
d
(a.u.); Medium acid peak area(a.u.); Weak acid peak area
(a.u.); Total NH3ꢀTPD peak area (a.u.); NH3 adsorption
quantity calculated by Pulsed Sampling.
e
f
The infrared spectra of adsorbed pyridine (PyꢀIR) onthe
catalysts after desorption at 150 oC after adsorbing a certain
amount of pyridine were displayed in Figure 13. Bands at 1450
and 1540 cmꢀ1 were attributed to be the pyridine adsorbed on
the Lewis acid and Brønsted acid sites, respectively.4c The
concentrations of Lewis (L) acid and Brønsted (B) acid sites at
1450 and 1540 cmꢀ129 were given in Table 4. The results
showed that both Brønsted and Lewis acid sites increased after
Pt and Re loading (Table 4, entries 2 vs. 1, 3 vs. 2), which was
benefit to glycerol dehydration, a key intermediate step for
hydrogenolysis of glycerol.3c
Figure 13 PyꢀIR spectra of the catalysts after desorption at 150
oC: (
a
) WO3/ZrO2, (
b) 2Pt/WO3/ZrO2, (c) 2Ptꢀ0.8Re/WO3/ZrO2.
Table 4 Acid amount on catalyst surface
entry
cat.a
Bb
Lc
Figure 12 1H MAS NMR spectra of (a)ꢀ(b) WO3/ZrO2, (c)ꢀ(d)
2Pt/WO3/ZrO2 and (e)ꢀ(f) 2Pt/WO3/ZrO2 catalysts with (red line) or
without (black line) hydrogen adsorption.
1
2
3
(I)
11.0
12.3
15.9
3.0
7.6
15.3
(II)
(III)
a Catalyst: (I)WO3/ZrO2,(II) Pt/WO3/ZrO2, (III) Ptꢀ0.8Re/WO3/ZrO2
;
Amount of surface acid on catalysts were calculated and
given in Table 3. Pt doping elevated the total acid amount on
WO3/ZrO2 surface (Table 3, entries 2 vs. 1). Although
2Re/WO3/ZrO2 had less total acid amount than 2Pt/WO3/ZrO2
(Table 3, entries 4 vs. 2), the total acid amount of 2Ptꢀ
0.8Re/WO3/ZrO2 increased (Table 3, entries 3 vs. 2), indicating
that the acidity of the catalyst was enhanced after the
introduction of ReOx. The increment was mainly caused by the
b Brønsted acid peak area (a.u.); c Lewis acid peak area (a.u.).
Conclusions
In conclusion, rhenium additives could largely improve the
Pt/WO3/ZrO2 catalytic activity for glycerol hydrogenolysis, giving
glycerol conversion in the almost quantitative 99.9% yield
and >95% selectivity of C3 alcohols, in which 1ꢀPO was the major
6 | J. Name., 2012, 00, 1-3
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product in 51.3% selectivity. Addition of rhenium made the catalyst
Surface area was obtained by N2 physisorption at ꢀ196 oC using a
so active that even reaction performed under atmosphere H2 pressure Micromeritics ASAP3020C automatic adsorption instrument. All
led to 96.8% glycerol conversion and 95.2% total selectivity of the samples were dried at 300 oC for 3 h under high vacuum prior to the
C3 compounds, in which acetol was obtained as the major product in physisorption measurements. The surface area was calculated using
63.1% selectivity. Further XRD, Raman, BET, CO chemisorption, the Brunauer, Emmett, and Teller (BET) method.
1
TEM, H2–TPR, XPS, NH3–TPD, H MAS NMR and PyꢀIR studies
Temperatureꢀprogrammed desorption of chemisorbed CO was
indicated that Re improved the catalyst by enhancing Pt dispersion performed in the same apparatus used for H2ꢀTPR. In this case, 0.1 g
and catalyst surface acidity. Compared with reported works, the of sample was reduced at 250 oC, then the sample was cooled to
advantages of this work are the complete glycerol conversion, the room temperature and purged with dry He (20 mL minꢀ1) for 1 h in
excellent C3 alcohol selectivity and the lowest H2 pressure. The order to remove any adsorbed hydrogen. After that, CO
complete glycerol conversion leads to very high capacity in chemisorption uptakes were measured by pulses of pure CO at room
industrial production; the excellent total C3 alcohol selectivity temperature.
prevents the generation of useless wastes in large scale preparation;
Hydrogen Temperature Programmed Reduction (H2ꢀTPR) was
the low hydrogen pressure reduces the equipment requirements and performed on a conventional apparatus with a thermal conductivity
energy consumption. In order to facilitate the readers to further detector (TCD). 0.1 g of sample was loaded in a quartz tube and the
1
understand the advantages of this work, we summarized the major reduction was carried out from 50 oC up to 700 oC (10 oC min− ) in a
1
references in the field in Table S6 in ESI and related comparisons 10% H2/Ar mixture with a flow rate of 25 mL min− .
and discussions were also made there. The 2PtꢀxRe/WO3/ZrO2
Temperature programmed desorption of NH3 (NH3ꢀTPD)
catalysts are of significant industrial value and further investigation analysis was conducted on an inꢀhouse constructed apparatus. The
on large scale applications are in progress in our laboratory.
catalyst sample (0.1 g) was first purged in Ar for 0.5 h at 450oC, and
then cooled to 100 oC and NH3 adsorption was carried out by passing
a 1% NH3/Ar mixture for 0.5 h. Any residual NH3 was removed in a
flow of dry Ar at the same temperature, the temperature was then
raised to 600 oC at a heating rate of 10 oC/min and desorption of NH3
was recorded by a TCD.
Experimental Section
Catalyst Preparation
PtꢀRe/WO3/ZrO2 catalysts were synthesized by sequential
Xꢀray photoelectron spectroscopy (XPS) measurement was
obtained using Multilab 2000 XPS system with a monochromatic
Mg Kα source and a charge neutralizer. All the binding energy were
referenced to the surface contaminated carbon (C1s=284.6 eV).
1H MAS NMR spectra were obtained with Bruker Avance III 400
wide cavity solid nuclear magnetic resonance spectrometer, with a
wetness impregnation method.
mꢀZrO2 was used as support, and
it was prepared by adding appropriate amounts of ammonia into
zirconium nitrate (Zr(NO3)4) to adjust pH value to 10. The
samples were then dried overnight at 110oC and calcined at
500oC in air for 4 h. The WO3/ZrO2 sample was prepared by
impregnation of
mꢀZrO2 with aqueous ammonium tungstate
1
4.0 mm double resonance probe. The resonant frequency of H was
((NH4)6(H2W12O40). nH2O), followed by calcination at 500 C
in air. The PtꢀRe/WO3/ZrO2 catalysts were fabricated by
impregnation of WO3/ZrO2 samples with aqueous solution of
chloroplatinic acid (HPtCl4) and ammonium perrhenate
(NH4ReO4). Impregnated samples were dried overnight at 110
oC and then calcined in air at 450 oC for 4 h. The Pt/WO3/ZrO2
catalyst and Re/WO3/ZrO2 catalyst were also prepared as above
by impregnation of WO3/ZrO2 with aqueous solution of
chloroplatinic acid (HPtCl4) or ammonium perrhenate
(NH4ReO4) respectively. The Pt/WO3/ZrO2 and Re/WO3/ZrO2
samples were dried and then calcined in air at 450 oC for 4 h.
The loading of Pt was fixed at 2 wt. % and the content of W
was fixed at 5 wt. % in all catalysts. These PtꢀRe/WO3/ZrO2
samples were denoted as 2PtꢀxRe/WO3/ZrO2, where x refered
to the rhenium content in weight percent (wt. %) in catalysts.
o
400 Hz and the π/2 pulse length was 2.5 ꢁs. All the samples were
used the rotor synchronous echo experiments. The chemical shift of
1H was calibrated by external standard method and adamantane was
defined as the standard sample with a chemical shift of 1.92 ppm
.
Before the test, a known amount of the samples was placed in a glass
tube which was connected to a vacuum line. The temperature was
gradually increased at a rate of 10 °C/min, and the sample was kept
at a final temperature of 300 °C at a pressure below 10ꢀ3 Pa over a
period of 2 h and then cooled. After the sample cooled to ambient
temperature, hydrogen was introduced to the sample for 2 h. Then
the physisorbed hydrogen was removed under vacuum at
a
temperature ca. 80 °C for 1 h. Finally, the NMR tube was flame
sealed. Prior to NMR measurements, the samples were filled into
NMR rotors with a KelꢀF endcap (cut with 20 grooves) under a dry
nitrogen atmosphere in a glove box.
Catalyst Characterization
Powder Xꢀray diffraction (XRD) patterns of the catalysts were
collected on were recorded on
diffractometer using Niꢀfiltered Cu Kα radiation (λ = 0.15418 nm)
with a scanning range (2θ) of 10oꢀ80o. The tube voltage was 40 kV
and the current was 40 mA. The patterns were compared with the
power diffraction files (PDF) by XpertꢀPro High Score tool.
Raman spectroscopy was recorded on a Renishaw Invia Raman
Microscope at room temperature. The 532 nm of the Ar laser was
employed as the exciting source with a power of 20 MW.
IR spectra of adsorbed pyridine (PyꢀIR) were measured with
VERTEX70 (Bruker) FTꢀIR spectrophotometer. The samples were
degassed in vacuum at 300 oC for 1 h, and then exposed to the
pyridine vapor for 30 min after cooling down to room temperature.
The PyꢀIR spectra were then recorded at 150 oC after applying
vacuum for 60 min.
a Philips X’pert pro Xꢀray
Catalytic Performance test
The hydrogenolysis of glycerol was carried out in a fixedꢀbed
reactor made of a stainless steel tube (length, 450 mm; external
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ARTICLE
Journal Name
390, 119; (
e
) L.ꢀJ. Liu, Y.ꢀH. Zhang, A.ꢀQ. Wang and T.
diameter, 22.0 mm; internal diameter, 11.0 mm). The catalyst (1.8 g,
20–40 mesh) was placed between two layers of quartz sands for each
test. Prior to reaction, the catalyst was activated in flowing H2 (30
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g
mL minꢀ1) from ambient to 250 C at the rate of 3 C minꢀ1 and
maintaining that temperature for 2h at atmospheric pressure. After
reduction, the system was cooled to 175 oC. 10 wt. % aqueous
solutions of glycerol were continuously pumped into the fixedꢀbed
reactor with a highꢀpressure pump at the rate of 2.4mL hꢀ1. Hydrogen
from a gas cylinder was depressurized to 2.5 MPa and its flow rate
was set by a mass flow controller giving a constant flow of 100 mL
minꢀ1.
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The conversion of glycerol and the selectivity of liquid products
were calculated based on the following equations:
m
Conversion of glycerol (%) = (ΣCꢀbased mol of all liquid product
n
t=t) /(Cꢀbased mol of glycerol t=0
)
o
Selectivity of liquid product (%) = (Cꢀbased mol of product) /
(ΣCꢀbased mol of all liquid product)
The liquid products and residual glycerol were cooled by the
condenser and analyzed by GC 5890C equipped with a flame
ionization detector (FID) and a capillary column (PEGꢀ20m).
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Acknowledgements
We thank Specialized Research Fund for the Doctoral
Program of Higher Education (SRFDPꢀ2012009111001),
NNSFC (21202141), Priority Academic Program Development
(PAPD) of Jiangsu Higher Education Institutions, Key Science
& Technology Specific Projects of Yangzhou (YZ20122029),
the Innovation Foundation of Yangzhou University
(2015CXJ009), the High Level Talent Support Project of
Yangzhou University and Yangzhou Nature Science
Foundation (YZ2014040) for financial support. We thank the
analysis centre of Yangzhou University for assistances.
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DOI: 10.1039/C6RA21198D
Table of Contents
Rhenium-promoted Pt/WO3/ZrO2: An efficient catalyst for aqueous glycerol hydrogenolysis
under reduced H2 pressure
Qing Tong, Anyi Zong, Wei Gong, Lei Yu,*and Yining Fan*
Re dopping improved the diepsesion of Pt in Pt/WO3/ZrO2 and enhanced the catalyst surface acidity. The
Pt-Re/WO3/ZrO2 had excellent performance in glycerol hydrogenolysis, affording glycerol conversion >99% and C3
alcohol selectivity >95%. The reactions were performed under reduced H2 pressure.