One-pot synthesis of 1,3-butanediol by 1,4-anhydroerythritol hydrogenolysis over a tungsten-modified platinum on silica catalyst

Article abstract of DOI:10.1039/d0gc00244e

Chemical production of 1,3-butanediol from biomass-derived compounds was first reported by 1,4-anhydroerythritol hydrogenolysis over a Pt-WO_x/SiO₂ catalyst. The reaction proceeded by ring opening hydrogenolysis of 1,4-anhydroerythritol followed by selective removal of secondary OH groups in 1,2,3-butanetriol, and an overall 1,3-butanediol yield up to 54% was then obtained. The performance of the Pt-WO_x/SiO₂ catalyst for 1,4-anhydroerythritol hydrogenolysis was closely correlated with that for glycerol hydrogenolysis to 1,3-propanediol. The optimized Pt-WO_x/SiO₂ (Pt: 4 wt% and W: 0.94 wt%) catalyst showed 57% yield of 1,3-propanediol.

Full text of DOI:10.1039/d0gc00244e

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DOI: 10.1039/D0GC00244E
COMMUNICATION
One-pot synthesis of 1,3-butanediol by 1,4-anhydroerythritol
hydrogenolysis over tungsten-modified platinum on silica catalyst
Lujie Liu,a Takehiro Asano,a Yoshinao Nakagawa,a,b,* Masazumi Tamuraa,b and Keiichi
Received 00th January 20xx,
Accepted 00th January 20xx
Tomishigea,b,
*
DOI: 10.1039/x0xx00000x
Chemical production of 1,3-butanediol from biomass-derived AHERY)14,22-26 as starting substrates since erythritol is easily
compounds was first reported by 1,4-anhydroerythritol accessible by fermentation in industrial scale27-29 and 1,4-AHERY
hydrogenolysis over Pt-WOx/SiO2 catalyst. The reaction proceeded can be derived from simple dehydration of erythritol.30 1,4-
by ring opening hydrogenolysis of 1,4-anhydroerythritol followed AHERY is a platform substrate, which can be converted into
by selective removal of secondary OH group in 1,2,3-butanetriol, valuable chemicals by various heterogeneous catalysis systems,
and an overall 1,3-butanediol yield up to 54% was then obtained. such as tetrahydrofuran (THF),14,31 1,4-BuD,25,26 3-
The performance of Pt-WOx/SiO2 catalyst for 1,4-anhydroerythritol hydroxytetrahydrofuran (3-HTHF),22 2-butanol (2-BuOH)23 and
hydrogenolysis was closely correlated with that for glycerol 2,5-dihydrofuran.24 In fact, we have proposed a two-steps route
hydrogenolysis to 1,3-propanediol. The optimized Pt-WOx/SiO2 (Pt: for 1,3-BuD synthesis, including selective hydrodeoxygenation
4 wt% and W: 0.94 wt%) catalyst showed 57% yield of 1,3- of 1,4-AHERY to 3-HTHF and subsequent hydrogenolysis to 1,3-
propanediol.
BuD (Scheme 1, route 1).22,32 Combining these two systems to a
one-pot process is difficult due to the big difference in reaction
conditions such as temperature and solvent. In addition, we
have shown that the main product of 1,4-AHERY hydrogenolysis
at low conversion is 1,2,3-butanetriol (1,2,3-BuT) over many
types of catalysts including Rh/SiO2, Rh-MOx/SiO2 (M = Mo, W,
Re), Pt-MoOx/SiO2, and Ir-ReOx/SiO2.23 It appears promising to
develop a one-pot synthesis of 1,3-BuD by ring opening of 1,4-
AHERY to 1,2,3-BuT and selective cleavage of secondary OH
group to 1,3-BuD by catalytic regioselective hydrogenolysis
(Scheme 1, route 2). To achieve higher yield of 1,3-BuD from
1,4-AHERY, the step of 1,2,3-BuT to 1,3-BuD should proceed
over catalyst with high selectivity.
Transformation of biomass derived feedstocks to high value-
added chemicals has been a hot topic over the past few decades
since biomass is regarded as a renewable resource for the green
chemistry.1-6 Diols are widely used as co-monomers in polymers
formation, and preparation of ethylene glycol, for example,
from cellulose7-9 and propanediols (PrDs) (glycerol selective
hydrogenolysis to 1,2-PrD10 and 1,3-PrD11-13) via biomass-based
hydroconversion is available using heterogeneous metal
catalysis. To date, the synthesis of chain butanediols (BuDs)
with internal OH group (1,2-, 2,3- and 1,3-BuD) is still of great
challenge by catalytic hydrodeoxygenation of biomass-based
platform chemicals, and high yield of the aforementioned C4
diols is not reported except cis-didehydroxylation of erythritol
to 1,2-BuD.14 1,3-BuD can be used for production of
polyurethane and polyester resin as a co-monomer.5 At present,
acetaldehyde condensation and hydrogenation,15 and Prins
condensation using propylene and formaldehyde followed by
hydrolysis16 are effective systems to obtain 1,3-BuD as well as
the biochemical route for preparation of 1,3-BuD.17 Both our
group and other groups have made some attempts in selective
conversion of erythritol18-21 and 1,4-anhydroerythritol (1,4-
Step 1: Pd-WOx/ZrO2, 1,4-dioxane solvent,
8 MPa H2, 473 K, 74% yield of 3-HTHF
HO
Route 1: Two steps
Step 2: Ir-ReOx/SiO2, H2O solvent, 8 MPa
H2, 373 K, 24% conv. and 81% selectivity
O
HO
OH
OH
Step 1
Step 2
3-HTHF
HO
OH
O
1,3-BuD
1,4-AHERY
HO
OH
Route 2: One-pot synthesis
1,2,3-BuT
This work
Scheme 1 Proposed reaction pathway of 1,4-AHERY to 1,3-BuD.
a. Address here Department of Applied Chemistry, School of Engineering, Tohoku
University, Aoba 6–6–07, Aramaki, Aoba–ku, Sendai, 980–8579, Japan. Email:
yoshinao@erec.che.tohoku.ac.jp, tomi@erec.che.tohoku.ac.jp.
b. Research Center for Rare Metal and Green Innovation, Tohoku University, Aoba
468–1, Aramaki, Aoba–ku, Sendai, 980–0845, Japan.
Electronic Supplementary Information (ESI) available: Experimental section,
literature survey (Table S1), XRD and XANES spectra (Figs. S1 and S2) and
supplementary reaction data (Fig. S3; Tables S2-S7). See DOI: 10.1039/x0xx00000x
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COMMUNICATION
Table 1 Catalytic performance of Pt-WOx/SiO2 related catalysts in the 1,4-AHERY hydrogenolysis
Journal Name
View Article Online
DOI: 10.1039/D0GC00244E
Selectivity / %
1,3-BuD 1,2,3-BuT 1-BuOH 2-BuOH 1,2-BuD 2,3-BuD 3-HTHF
W/Pt Conv.
Entry
Catayst
ratio
-
0.063
0.13
0.25
0.5
1
/ %
<1
5
25
60
26
5
Others
1
2
3
4
5
4 wt% Pt/SiO2
Pt-WOx/SiO2
-
-
-
-
<1
2
2
-
-
3
4
7
8
-
-
-
<1
1
5
1
-
-
2
1
<1
<1
2
22
24
38
25
21
-
68
66
41
60
54
-
4
3
5
2
5
-
1
2
2
1
-
6
7a
15
-
2
-
WOx/SiO2
Physical
mixture
-
<1
-
-
8b
-
33
13
82
<1
3
-
1
2
-
Reaction conditions: 1,4-AHERY = 0.5 g, H2O = 4 g, Wcat = 0.2 g, P(H2) = 8 MPa, T = 413 K, t = 24 h.
a0.94 wt% WOx/SiO2. bPhysical mixture: 0.2 g of 4 wt% Pt/SiO2 + 0.2 g of 0.94 wt% WOx/SiO2.
t / h = 1 24 1 24 48 1 1 12a
1
8b 24b 4c 8c
1 1 24 48 1 48 1 1 24 1 1 1
literature studies were quite low, even considering the
moderate or high yield of 1,3-PrD from glycerol over the same
catalyst. In this work, we developed an effective and reusable
heterogeneous Pt-WOx/SiO2 catalyst with low W amount (W:
0.94 wt%, Pt/W = 4, molar ratio) for 1,3-BuD production with
high yield (54%) by 1,4-AHERY hydrogenolysis route. The
catalyst exhibits high 1,3-PrD yield (57%) at relatively low
reaction temperature compared to other works for Pt-WOx
catalysts in glycerol hydrogenolysis (Table S1). The performance
of 1,4-AHERY hydrogenolysis to 1,3-BuD and that of glycerol to
1,3-PrD over various Pt-WOx/SiO2 was closely correlated.
100
Others
3-HTHF
2,3-BuD
1,2-BuD
80
60
40
20
0
2-BuOH
1-BuOH
Conv.
1,3-BuD
1,2,3-BuT
I
P
I
R
P
r
I
r
r
-
R
d
-
R
-
-
Mo Re
- Mo
t
h
-
W
W
R
u
Re
Pt-M/SiO2
-
-
W
e
-
Mo
W
e
-
O
O
W
O
O
O
O
/
O
/
S
x
S
x
/
r
u
/
x
x
S
/
/
x
x
S
i
S
i
O
i
/
O
O
i
x
S
O
t
i
l
e
Pd-M/SiO2 Ir-M/SiO2
i
O
i
O
,
The tungsten modified group 8 noble metals (Pt, Ir, Rh, Ru and
Pd) on SiO2 catalysts were examined with fixed ratio (0.25) of
W/noble metal in 1,4-AHERY hydrogenolysis (Fig. 1). Catalysts
were prepared by sequential impregnation method and details
about reaction procedure are shown in Supporting Information.
The 1,3-BuD was only detected over Pt-WOx/SiO2 and Ir-
WOx/SiO2 catalysts whereas other WOx-modified ones were not
effective to obtain the desired 1,3-BuD. The other product over
these catalysts was mainly the possible intermediate of 1,2,3-
BuT. However, the selectivity to 1,3-BuD was not increased over
Ir-WOx/SiO2 even at longer reaction time. Next, the Ir-
ReOx/rutile catalyst which is the most active one in glycerol
hydrogenolysis to 1,3-PrD13 was also tested in 1,4-AHERY
hydrogenolysis. The 1,3-BuD yield was less than 20%, and large
amount of 2-BuOH was co-produced due to the
overhydrogenolysis, which was similar to the case of Ir-ReO-
x/SiO2 in 1,4-AHERY hydrogenolysis.23 We further tested
catalysts modified with other oxophilic metals (Mo, Re and W)
in this reaction. The Pt-MoOx/SiO2 showed some activity, but
the selectivity was unsatisfactory. In addition, the Rh-WOx, Pt-
ReOx, Pd-MoOx and Ir-MoOx/SiO2 catalysts gave some activity.
About 50% selectivity to 1,2,3-BuT was detected together with
certain amount of butanols. However, only trace amount of 1,3-
BuD was observed, indicating that the poor regioselectivity over
these catalysts and the butanols were produced by
hydrogenolysis of 1,2-, 2,3-BuD and/or 3-HTHF. Therefore, the
WOx-modified Pt catalyst was selected for further study. Table
1 lists the effect of W amount at fixed Pt loading amount (4 wt%)
on 1,4-AHERY hydrogenolysis over Pt-WOx/SiO2. The catalytic
performance showed a volcano-type dependence on W amount
at the W/Pt ratio from 0.063 to 1 (entries 2-6), and catalyst with
2
2
2
r
e
2
2
2
f
.
2
3
Fig. 1 Catalytic performance of hydrogenolysis of 1,4-AHERY
over the screened catalysts (Noble metal: 4 wt%, M = W, Mo
and Re, M/Noble metal = 0.25, molar ratio). Reaction
conditions: 1,4-AHERY = 0.5 g, H2O = 5 g, Wcat = 0.1 g, P(H2) = 8
MPa, T = 413 K, t = 1 h. a: T = 433 K. b: 1,4-AHERY = 1 g, H2O = 4
g, Wcat (4 wt% Ir, Re/Ir = 1) = 0.1 g, P(H2) = 8 MPa, T = 393 K.23 c:
Pre-reduction by H2 flow at 573 K for 1 h.
On the other hand, glycerol hydrogenolysis to 1,3-PrD has
been intensively investigated,33-36 which reaction itself is a very
important one in biomass refinery and can be a model reaction
for 1,2,3-BuT hydrogenolysis to 1,3-BuD. The Pt-based catalysts,
especially combined with WOx species (4–38 wt% W in most
cases, Table S1), and Ir-based catalysts, particularly promoted
by ReOx species, showed high selectivity to 1,3-PrD (up to 70%)
in glycerol hydrogenolysis.11-13 There are limited reports for 1,4-
AHERY hydrogenolysis over Pt- and Ir-based catalysts. We
reported that Ir-ReOx/SiO2 catalyst gave 23% selectivity to 1,3-
BuD at 63% 1,4-AHERY conversion, while that catalyst showed
maximum 38% yield of 1,3-PrD in glycerol hydrogenolysis.23
Yang and Cao et al. recently reported that IrOx/H-ZSM-5 catalyst
converted 1,4-AHERY into THF with 85% selectivity at 64%
conversion, while such catalyst selectively converted glycerol to
1,3-PrD at initial stage (75% selectivity) and the maximum 1,3-
PrD yield was 28%.31 Shishido et al. tested Pt/WO3/Al2O3
catalyst, and the 1,4-AHERY conversion was about 1 order lower
than that in glycerol hydrogenolysis with the main product of
THF whereas high 1,3-PrD selectivity (45%) in glycerol
conversion was obtained.37,38 The 1,3-BuD yields of these
2 | Green. Chem., 2020, 00, 1-5
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3-HTHF
Others
100
1,4-AHERY hydrogenolysis, the total selectivity to 2-BuOH + 1,3-
BuD + 1,2,3-BuT was almost constant (Table S3). The 2-BuOH
View Article Online
DOI: 10.1039/D0GC00244E
2,3-BuD
1,2-BuD
2-BuOH
1-BuOH
80
60
40
20
0
was also prone to be produced at higher W amount and the
selectivity to 1,3-BuD + 1,2,3-BuT became lower. Considering
that 2-BuOH is a by-product in overhydrogenolysis of 1,3-BuD
as discussed later, it seems that the catalyst structure tuned by
W amount affects each reaction step to a different extent in 1,4-
AHERY hydrogenolysis. Both Pt/SiO2 and WOx/SiO2 hardly
catalyzed the 1,4-AHERY hydrogenolysis, and the physical
mixture one (entry 8) gave much lower 1,3-BuD yield relative to
1,2,3-BuT
1,3-BuD
Conv.
R
P
H
C
S
A
2
Z
r
C
M
i
u
2
l
e
-
Z
O
2
g
O
O
2
Support
t
5
O
O
2
i
S
l
e
3
M
-
5
the
4 wt% Pt-WOx/SiO2 (W/Pt = 0.25) catalyst. The
Fig. 2 Effect of support on the 1,4-AHERY hydrogenolysis over 4
wt% Pt-WOx based catalysts (W/Pt = 0.25). Reaction conditions:
1,4-AHERY = 0.5 g, H2O = 4 g, Wcat = 0.2 g, P(H2) = 8 MPa, T = 413
K, t = 24 h.
aforementioned results suggest that the synergistic effect
between Pt and WOx species has profound influence on the
catalytic performance, and such synergy is sensitive to W
amount.
Conv.
1,3-PrD
1,2-PrD
1-PrOH
Conv.
1,3-BuD
1,2-BuD
3-HTHF
1,2,3-BuT
1-BuOH
100
80
60
40
20
0
100
80
60
40
20
0
2-PrOH
Acetone
Propane
2-BuOH
2,3-BuD
Others
(B)
(A)
XRD patterns of related Pt-WOx/SiO2 catalysts showed that
the bulk Pt was in metallic state after calcination or catalytic
use. The Pt dispersion was promoted by addition of W, and the
WO3 species was solely observed at W/Pt ratio of 1 over 4 wt%
Pt-WOx/SiO2 (Fig. S1). However, the change of Pt particle size
was small in comparison with the activity difference (Table 1).
Therefore the synergy between Pt and WOx species whose
structure was changed with the W amount is responsible for the
hydrogenolysis catalysis. The average particle size of Pt of
physical mixture sample (Pt/SiO2 + WOx/SiO2) and standard
catalyst (Pt-WOx/SiO2) after reaction was comparable (4.4
nm), which was smaller than the Pt/SiO2 (7.0 nm). Probably, the
presence of some leachable WOx species suppresses the Pt
particles aggregation during the reduction and reaction. The
XANES spectra were further employed to determine the valence
of both Pt and W over Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25)
catalyst (Fig. S2). The Pt species were partially reduced after
calcination, and transformed into Pt0 after reduction (L, 473).
The W L3-edge XANES spectrum of calcined catalyst was similar
to WO3 and precursor (NH4)6H2W12O40nH2O. After reduction,
the white line intensity was between WO2 and WO3, indicating
that a small amount of W was reduced.
The support also has drastic effect on the activity of bimetallic
catalysts based on our previous reports.13,14 Therefore the
activity of Pt-WOx (Pt: 4 wt%, W/Pt = 0.25) pairs dispersed on a
series of supports was then investigated (Fig. 2). SiO2 was by far
the best support in views of both activity and selectivity.
Activated carbon, MgO, H-ZSM-5, CeO2, ZrO2 and Al2O3
supported Pt-WOx catalysts gave almost no activity. Probably,
the Pt and WOx species were individually dispersed on these
supports since no activity was also observed over Pt/SiO2 or
WOx/SiO2 catalyst. The conversion over rutile TiO2 supported
catalyst was higher than that over P25 TiO2. With respect to the
products distribution, the selectivity to 1,3-BuD + 1,2,3-BuT was
almost the same over SiO2 and TiO2 support. However, 2-BuOH
was more favourable to produce over TiO2 supported catalysts
even at lower conversion level. This result implies that the
overhydrogenolysis decreases the 1,3-BuD yield. The support
effect on glycerol hydrogenolysis was consistent with that on
1,4-AHERY (Fig. S3). The overhydrogenolysis products of 1-PrOH
and propane with high proportion were detected over TiO2
supported catalysts, decreasing the 1,3-PrD selectivity. In some
57% yield
54% yield
0
10 20 30 40 50 60 70 80 90 100
0
5
10
15
t / h
20
25
30
t / h
Fig. 3 Time course of the (A) 1,4-AHERY and (B) glycerol
hydrogenolysis over 4 wt% Pt-WOx/SiO2 (W/Pt = 0.25). Reaction
conditions: 1,4-AHERY = 0.5 g or glycerol = 1 g, H2O = 4 g, Wcat
=
0.2 g, P(H2) = 8 MPa, T = 413 K. The detailed data are provided
in Tables S6 and S7.
W/Pt ratio of 0.25 gave the highest activity. The volcano-type
dependence on W amount has been also reported for Pt-WOx
based catalysts in cleavage of C-O bond although the activity
was generally maximized at relatively high W amount (e.g. 78
wt%).37,39 With small amount of W, fewer WOx clusters are
available for 1,4-AHERY to anchor; increasing the W loading
amount would lead to higher coverage of WOx species on Pt
metal surface, and thus lower the ability for H2 activation. In
both cases, the activity is decreased. The main products over Pt-
WOx/SiO2 were 1,3-BuD and 1,2,3-BuT, and the latter is a
possible intermediate of 1,3-BuD formation. With higher W/Pt
ratio above 0.25, the selectivity to 2-BuOH which is an
overhydrogenolysis product, was increased even at decreasing
conversion level. The effect of W amount on glycerol
hydrogenolysis was also investigated and results are shown in
Table S2. The activity trend gave even stronger dependency on
W amount in glycerol conversion, and Pt-WOx/SiO2 (W/Pt =
0.25) was the most active one for both reactants. In the
optimization of Ir-ReOx/SiO2 catalyst, Mushrif and et al.
proposed that the reaction pathway was altered with increasing
the Re/Ir ratio.40 Higher coverage of ReOx clusters on Ir particles
facilitated thermodynamically preferred product of 1,2-PrD due
to the Brønsted acidic ReOx clusters. However, such phenomena
was not observed, and the selectivity to 1,2-PrD + 2-PrOH was
even decreased at W/Pt ratio from 0.13 to 0.5 (Table S2). That
means that the dominant route was not changed over catalysts
modified by different W amount. Then we compared the
activity over these catalysts at same conversion level (25%) in
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Journal Name
cases of Pt-WOx (W:  8 wt%) supported on ZrO2 and Al2O3 overhydrogenolysis of 1,3-PrD was slower than that of 1,3-BuD.
View Article Online
catalysts, they were active in glycerol hydrogenolysis to 1,3- This result agrees with the conveDrsOioI:n10.1t0e3n9/dDe0nGcCy002th44aEt
PrD.35,36,41-43 The much lower activity in our case may be due to overhydrogenolysis of 1,3-BuD was more favorable relative to
the small W amount on ZrO2 and Al2O3 support.
1,3-PrD (Fig. 3). An interesting point is that the hydrogenolysis
We compared the hydrogenolysis of 1,4-AHERY and glycerol of 1,3-BuD gave 2-BuOH as the main product (entry 5, 78%
activities. Fig. 3A presents the time course of 1,4-AHERY selectivity). This result indicates that the carbenium ion with the
hydrogenolysis. At short reaction time, the main product was assistance of Brønsted acidic sites is not involved in the C-O
1,2,3-BuT, and another C-O hydrogenolysis product 3-HTHF was bond dissociation in 1,3-BuD, and further study is required to
hardly observed. The selectivity to 1,3-BuD was increased and elucidate the reaction mechanism. For erythritol
that to 1,2,3-BuT was decreased with the reaction progress. The hydrogenolysis, 1,4-BuD was the main product. The conversion
maximum 1,3-BuD yield was 54% at 80 h, which was the highest routes from erythritol using Pt-WOx/SiO2 are summarized in
value among one-pot synthesis using biomass-derived Scheme 2.
chemicals. It is an alternative green route to produce 1,3-BuD
since the yield is comparable to the reported tandem reaction
Conclusions
route by Prins condensation using propylene and formaldehyde
In conclusion, the optimized Pt-WOx/SiO2 with low W loading
and followed by hydrolysis (1,3-BuD yield: 60%) over CeO2
amount was an effective catalyst for 1,4-AHERY hydrogenolysis
catalyst.16 The time course of glycerol hydrogenolysis is also
to 1,3-BuD. Ir-based catalysts such as Ir-ReOx/SiO2 and Ir-
shown in Fig. 3B. The highest 1,3-PrD yield was 57% at 24 h and
ReOx/rutile were difficult to give high yield of 1,3-BuD due to
the maximum 1,3-PrD productivity (P1,3-PrD) was 4.8 g gPt–1 h–1 at
the overhydrogenolysis to butanols. The reaction is composed
82% conversion and 64% selectivity to 1,3-PrD (12 h), which was
of 1,4-AHERY to 1,2,3-BuT and successive hydrogenolysis of
in top level among all the reported Pt-WOx based systems (Table
1,2,3-BuT to 1,3-BuD. The performance of Pt-WOx catalysts for
S1). Both high 1,3-PrD yield and high productivity can be
1,4-AHERY hydrogenolysis to 1,3-BuD was significantly related
achieved over Pt-WOx/SiO2 even with such low W amount. The
to that for glycerol hydrogenolysis to 1,3-PrD. The Pt-WOx
overhydrogenolysis of 1,3-PrD to 1-PrOH was suppressed while
catalysts with higher activity and selectivity in glycerol
that of 1,3-BuD to BuOHs gradually proceeded. The tendency of
hydrogenolysis showed also high performance in 1,4-AHERY
easier overhydrogenolysis in 1,4-AHERY than glycerol might
hydrogenolysis to 1,3-BuD. The highest yield of 1,3-BuD and 1,3-
cause the low yield of 1,3-BuD in the previous studies.
PrD from 1,4-AHERY and glycerol was 54% and 57%,
Moreover, the Pt-WOx/SiO2 catalyst can be reused in 1,4-AHERY
respectively. The W amount much affected the activity, showing
hydrogenolysis at least three times without decreasing of
volcano-curve dependence. On the other hand, Pt particle size
activity or selectivity (Table S4). The leaching of Pt was
was not so changed by the W amount. The synergy of Pt
negligible (Table S5) in the solution after catalytic usage.
particles and WOx species should be present, and further study
Although small amount of leached WOx species was detected, it
is ongoing to clarify the catalyst structure and reaction
became smaller in the repeated uses. Considering the stable
mechanism.
activity in reuses, the loss of W has little effect on the active site
HO
of Pt-WOx/SiO2.
The optimized Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25) catalyst
O
3-HTHF
was applied to the hydrogenolysis of related alcohols (Table 2).
In the case of triols (entries 2 and 3) hydrogenolysis, 1,2,4- has
minor
OH
HO
OH
OH
major
major
higher activity than that of 1,2,3-BuT. It can be explained by the
higher steric hindrance between 1,2,3-BuT and active site over
catalyst surface. The neighboring OH group to the primary OH
group possesses higher reactivity (entries 4-7 and 12-13), and
cleavage of C-O bond is difficult to proceed over mono-alcohols
(entries 8-9). Hydrogenolysis of 3-HTHF gave high selectivity to
1,3-BuD (90%, entry 10) at relatively high conversion level
(40%). Both 1,3-PrD and 1,3-BuD have lower reactivity, which is
consistent with the obtained high yield (entries 5 and 13). The
HO
HO
OH
O
OH
1,4-Anhydroerythritol
1,2,3-BuT
1,3-BuD
2-BuOH
minor
acid
-H2O
minor
HO
OH
1-BuOH
OH
OH
major
OH
HO
HO
HO
OH
Erythritol
OH
1,2,4-BuT
1,4-BuD
Scheme 2 Reaction routes of 1,4-AHERY and erythritol over 4
wt% Pt-WOx/SiO2 (W/Pt = 0.25) catalyst.
Table 2 Catalytic performance of 4 wt% Pt-WOx/SiO2 (W/Pt= 0.25) catalyst in the hydrogenolysis of related alcohols
Entry
1
Substrate
Conv. / %
Products (selectivity (%))
1,2,3-BuT (41), 1,3-BuD (38), 1,2-BuD (2), 2,3-BuD (5), 2-BuOH (7), 1-BuOH (2), 3-HTHF (5),
others (<1)
1,4-AHERY
60
2
3
4
5
6
1,2,3-BuT
1,2,4-BuT
1,4-BuD
1,3-BuD
1,2-BuD
34
99
14
12
97
1,3-BuD (67), 1,2-BuD (<1), 2,3-BuD (10), 2-BuOH (14), 1-BuOH (8), others (2)
1,4-BuD (71), 1,3-BuD (8), 2-BuOH (1), 1-BuOH (18), others (2)
1-BuOH (97), others (3)
2-BuOH (78), 1-BuOH (21), others (1)
1-BuOH (92), 2-BuOH (7), others (<1)
4 | Green. Chem., 2020, 00, 1-5
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Journal Name
COMMUNICATION
7
2,3-BuD
2-BuOH
1-BuOH
3-HTHF
Glycerol
1,2-PrD
1,3-PrD
8
<1
1
40
56
60
8
2-BuOH (93), butanone (6), n-butane (1)
Butanone (61), n-butane (39)
Butyraldehyde (12), n-butane (88)
View Article Online
DOI: 10.1039/D0GC00244E
8a
9a
10
11b
12b
13b
1,3-BuD (90), 2-BuOH (4), 1-BuOH (4), others (2)
1,3-PrD (65), 1,2-PrD (4), 1-PrOH (17), 2-PrOH (12), acetone (1), propane (1)
1-PrOH (88), 2-PrOH (9), acetone (<1), propane (2)
1-PrOH (96), propane (4)
1,2,4-BuT (24), 1,2,3-BuT (12), 1,4-BuD (40), 1,3-BuD (13), 1,2-BuD (1), 2,3-BuD (<1), 1-BuOH
(6), 2-BuOH (4)
14
Erythritol
83
Reaction conditions: Substrate = 0.5 g, H2O = 4 g, Wcat = 0.2 g, P(H2) = 8 MPa, T = 413 K, t = 24 h.
a: t = 48 h. b: substrate = 1 g, t = 8 h.
20. A. Sadier, N. Perret, D. Da Silva Perez, M. Besson and C. Pinel,
Appl. Catal. A, 2019, 586, 117213.
Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
This work was supported by JSPS KAKENHI 18H05247. Part of
this work was carried out on commission by Ministry of the
Environment, Japan, as “Demonstration project for plastics
resource circulation system for decarbonized society”. Lujie Liu
thanks the China Scholarship Council (CSC) for financial support.
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