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162
Chapter 7.
One-pot synthesis of THF from but-2-ene-1,4diyl acetate (1,4-DABE) over bifunctional
rhodium silica-alumina catalysts
163
7.1. Introduction
Tetrahydrofuran (THF) is a common raw material used in in the production of poly
tetramethylene ether glycol (PTMEG), a component of polyurethane and a great
industrial solvent used in Vinyl chloride (PVC), pharmaceuticals and coatings. THF
was mainly a product of the petrochemical industry, and about million tons of THF are
produced annually. On the other hand, with the deepening of the research on biomass
in recent years, the methods using biomass resources have also been developed, and
furfural was used as the main raw material[1,2]. In addition, a synthesis method of THF
from 1,4-anhydroerythritol (1,4-AHERY), a dehydration product of biomass-derived
erythritol was also reported[3]. Although there are many specific processes for the mass
production, most are based on C4 base chemicals. For example, in the current
Mitsubishi Chemical Corporation (MCC) method[4,5], a four-step process from buta1,3-diene was used (Fig. 1a). In the process, the buta-1,3-diene was first transformed to
but-3-ene-1,2-diyl diacetate (1,4-DABE) through acetoxylation, and subsequent
hydrogenation, hydrolysis, and condensation take place to obtain the final product. The
yield of each step is relatively high, but the complex process, high investment, and large
amounts of wastewater limit the sustainability of the process. Therefore, in addition to
using more environmentally friendly raw materials like biomass, sustainable
improvements and innovations in existing processes are also of great value. In the MCC
method, if the multi-step process of THF could be replaced by a one-pot synthesis, huge
economic and environmental benefits could be achieved.
One-pot synthesis method in catalysis requires the catalysts to provide multiple
functions simultaneously[6,7]. Considering the unit step in the current MCC method,
the acid function and hydrogenation function of catalysts should play dominant roles;
thus, bifunctional heterogeneous catalysts need to be developed. The general concept
of bifunctional heterogeneous catalysis is that there are two distinct types of active sites
that function in tandem. Normally, the two sites are expected to catalyze different steps
within an overall reaction. In principle, the two sites could participate in the same step,
for example, acting on different parts of the adsorbed reactant molecule, as in a
164
consistent reaction [8]. In fact, bifunctional catalysts have been widely researched in
various direct synthesis of valued-added chemicals, such as hydrodeoxygenation[9,10],
hydroisomerization[11,12], and dehydrocyclization[13,14].
A typical model of bifunctional catalysts was metal species supported by zeolites
or mesoporous materials with rich porosities and acidities [15–18]. Noble metals (Pt,
Pd, Ru, Rh) and transition metals (Ni, Co, Fe) were widely used as active hydrogenation
centers, and even show great efficiencies under low metal loadings. Therefore,
supported bifunctional catalysts should consist of active metal nanoparticles with
hydrogenation capacities and supports of zeolite or mesoporous materials. In addition,
the synergistic effect of metal and zeolite/mesoporous materials over bifunctional
catalysts was normally existed and the adjustment to specific chemical reaction
pathway could enhance the conversion and the selectivity of final products. [19–22].
Herein, a direct one-pot synthesis method of THF from 1,4-DABE was realized
using bifunctional catalysts Rh0/Al-MCM-41 (Fig. 1b). A yield around 60% was
obtained using the optimized catalysts, and another main product was butane-1,4-diyl
diacetate (1,4-DAB) in a yield around 30%, which could be further used in the synthesis
of THF. The characterization over the catalysts showed that supported Rh nanoparticles
(NPs) were in small sizes and highly dispersed. In addition, a synergistic effect in the
acidity occurred, the loading of Rh NPs enhanced the strong acid sites.
AcO
AcO
[cat.]
AcOH, O2
a. Current process of THF synthesis (MCC method)
H 2O
OAc [cat.]
AcO
OH
[ca
H2
.]
at
[c
t.]
this research
H 2, H 2O
OAc
[cat.]
b. This research: One-pot synthesis of THF
AcO
OAc
Rh0/Al-MCM-41
H2 (0.5 MPa), 150 °C,
H2O (1 eq.)
AcO
OAc
Figure 1. The current MCC process (a) and the new one-pot process (b) to THF
synthesis.
165
7.2. Experimental
7.2.1. Materials
Rhodium(III) chloride trihydrate (RhCl3·3H2O) and ruthenium(III) chloride
trihydrate (RuCl3·3H2O) were purchased from Sigma Aldrich Ltd. Chloroplatinic acid
hexahydrate (H2PtCl6·6H2O) was purchased from Furuya Metal Co., Ltd. Palladium
nitrate (Pd(NO3)2) were purchased from Tanaka Precious Metals Co., Ltd. Nickel(II)
nitrate hexahydrate (Ni(NO3)2·6H2O), Cobalt(II) nitrate hexahydrate (Co(NO3)2·6H2O),
and Iron(III) nitrate enneahydrate (Fe(NO3)3·9H2O) were purchased from FUJIFILM
Wako Pure Chemical Corp.
Al-MCM-41 and Mont-K10 were purchased from Sigma Aldrich Ltd. Al2O3 (JRCALO-10), Nb2O5 (JRC-NBO-1), and MgO (JRC-MGO-4, A2000) were reference
catalysts supplied by the Catalysts Society of Japan. HS690 was purchased from
Daiichi Kigenso Kagaku Kogyo Co., Ltd. SiO2 (CARiACT Q-10) was purchased from
Fuji Silysia Ltd. 1,4-DABE was provided by Mitsubishi Chemical Corporation and
used as received. Hydrotalcite was purchased from FUJIFILM Wako Pure Chemical
Corp.
7.2.2. Preparation of catalysts
Supported catalysts with a loading of 1 wt% were generally prepared by the
impregnation method. The precursor was dissolved in distilled water (The amount of
distilled water used for different supports was as follows. Mont-K10: 0.5 mL; AlMCM-41: 1 mL; Al2O3: 1.5 mL; SiO2: 1.5 mL; HS690: 1 mL; Nb2O5: 0.5 mL;
Hydrotalcite: 1 mL; MgO: 0.5 mL). The support power (1.0 g) was added to the solution,
and the mixture was stirred for 20 min at room temperature. After the impregnation was
completed, residual distilled water was removed by drying at 70 °C overnight. The
catalysts were calcined at 400 °C for 2 h. Then they were reduced in a flow of H2 (20
mL/min) at 300 °C for 1 h. The obtained catalysts were directly used for catalytic
reactions without further treatment.
In the preparation of Pt/Al-MCM-41 and Pd/Al-MCM-41, H2PtCl6 aqueous
166
solution (Pt: 20 g/L; 505 μL) or Pd(NO3)2 aqueous solution (Pd: 200 g/L, 51 μL) was
diluted in 1 mL distilled water. Al-MCM-41 (1.0 g) was added to the aqueous solution,
and the following procedures were the same as those of the general method.
Ni/Al-MCM-41, Co/Al-MCM-41, and Fe/Al-MCM-41were prepared by the same
method, and changed temperatures of 600 °C, 300 °C, and 600 °C were used in the
reduction process, respectively, which were determined by the temperatureprogrammed reduction of H2 (H2-TPR)
7.2.3. Characterization
High-angle annular dark-field scanning transmission electron microscopy
(HAADF-STEM) images were performed with a JEOL JEM-ARM200F. H2-TPR was
performed by a BELCAT instrument equipped with a thermal conductivity detector
(TCD). Temperature-programmed desorption of NH3 (NH3-TPD) was measured by a
BELCAT instrument equipped with a BELMASS quadrupole mass spectrometer. 200g
catalyst was placed in a glass tube and pretreated at 250 °C for 1 h under a He flow.
The adsorption of NH3 was performed at 100 °C for 1 h with a flow 5% NH3 in He at
50 mL/min. Then a flow of He at 50 mL/min was performed at 100 °C for 1 h. During
the test, the samples were heated to 800 °C at 10 °C /min, under a He flow of 50 mL/min.
The mass spectrometer for NH3 desorption was collected by m/z = 17.
Conversions and yields of the compounds discussed were detected by gas
chromatography (GC) using an Agilent GC 6850 Series II instrument equipped with a
flame ionization detector (FID) and a J&W HP-1 column. GC mass spectrometry (GCMS) analysis was performed to determine the products using a Shimadzu GCMSQP2010 SE.
7.2.4. General Procedure for the Catalytic Reactions
A mini-autoclave (10 mL) was charged with 1,4-DABE (1 mmol), catalysts (50
mg), distilled water (1 mmol), and a magnetic stirring bar. Then, the autoclave was
purged and filled with H2 until the pressure reached 0.5 MPa, and then stirred at 150 °C
for 24 h. After the reaction, the mixture was filtered, and the filtrate was analyzed by
GC using tridecane as an internal standard.
167
7.3. Results and conclusions
In the catalyst screening section, mesoporous materials supported Ru NPs was
examined (Table 1, entries 1–6). High conversions were obtained when using these
catalysts, and a yield of 50% was achieved over the Ru/Mont-K10 catalysts for 48 h.
However, limited yields of THF were obtained with the Ru/Al2O3 and Ru/SiO2, which
should be caused by the relatively low acidities compared with those of Ru/Mont-K10
and Ru/Al-MCM-41. In addition, supported Rh NPs catalysts were also investigated
(entries 7–9), and Rh/Al-MCM-41 showed a yield of 55%.
Table 1. Catalyst screening for the one-pot synthesis of THF from 1,4-DABE.
AcO
OAc
1 mmol
Catalyst
H2 (0.5 MPa), 150 °C, 24 h
H2O (1 eq.)
1a
AcO
OAc
AcO
1c
1b
Conv.a/% Yield(1a)a/% Yield(1b)a/% Yield(1c)a/%
Entry
Catalyst
Ru/Mont-K10
>99
29
33
12
2b
Ru/Mont-K10
>99
50
10
17
Ru/Al-MCM-41
>99
28
41
13
4b
Ru/Al-MCM-41
>99
33
21
15
Ru/Al2O3
91
49
18
Ru/SiO2
96
n.d.
50
26
Rh/Mont-K10
>99
20
29
23
Rh/Al-MCM-41
99
55
33
9c
Rh/Al-MCM-41
98
21
37
14
10
Pt/Al-MCM-41
99
12
25
33
11
Pd/Al-MCM-41
97
12
12
Ni/Al-MCM-41
>99
33
12
13
Co/Al-MCM-41
>99
13
12
14
Fe/Al-MCM-41
98
11
22
13
Determined by GC analysis using tridecane as an internal standard.
Reaction time: 48h
Catalyst: 25 mg
168
Moreover, other metals, such as Pt, Pd, Ni, Co, and Fe with reduction capacities
were also examined based on the Al-MCM-41 support (entries 10–14). However, only
low yields were obtained with Pt/Al-MCM-41 and Pd/Al-MCM-41 catalysts. On the
other hand, Ni/Al-MCM-41 provided a yield of THF in 33%, which was higher than
that of Ru/Al-MCM-41. No satisfactory yields were obtained when the Co/Al-MCM41 and Fe/Al-MCM-41 were tested. In addition to the target product THF and
intermediate 1,4-DAB, a byproduct butyl acetate (BUA) was also detected. The highest
selectivity of THF AND 1,4-DAB was realized with the Rh/Al-MCM-41 among the
examined catalysts.
Because of the great yield of Rh/Al-MCM-41 in the initial screening, a further
investigation on the supports was conducted (Table 2). Considering the properties of
the supports, the high strong Brønsted acidity and high specific surface area seem to
facilitate the reaction. In addition, no production of THF was detected when using the
catalysts prepared from basic supports.
Table 2. Results of the one-pot synthesis from 1,4-DABE using Rh NPs on different
supports.
AcO
OAc
1 mmol
Catalyst
H2 (0.5 MPa), 150 °C, 24 h
H2O (1 eq.)
1a
AcO
OAc
AcO
1c
1b
Conv.a/% Yield(1a)a/% Yield(1b)a/% Yield(1c)a/%
Entry
Catalyst
Rh/Al-MCM-41
99
55
33
Rh/Mont-K10
>99
20
29
23
Rh/HS690
99
17
31
15
Rh/Nb2O5
99
13
20
23
Rh/Hydrotalcite
>98
n.d.
13
Rh/MgO
98
n.d.
27
23
Determined by GC analysis using tridecane as an internal standard.
Because the Rh/Al-MCM-41 showed superior activity in this one-pot synthesis of
THF from 1,4-DABE. The morphology and particle size distribution of the optimized
169
Rh/Al-MCM-41 catalysts were measured by HAADF-STEM (Fig. 2). A narrow
distribution of Rh NPs within 0.5 to 2 nm reveals that the Rh NPs were high dispersed
on the surface of Al-MCM-41, and the average particle size was 1.3 nm.
1.3 ± 0.2 nm
Figure 2. BF-STEM images and histograms of the particle sized of Rh/Al-MCM-41.
Afterwards, the effect of hydrogen pressure in the one-pot synthesis of THF was
investigated with Rh/Al-MCM-41 (Fig. 3). A hydrogen pressure of 0.5 MPa brought
the best THF yield and selectivity within the pressure range from 0.1 to 5.0 MPa. The
results showed that a yield a 51% could be obtained even under 0.1 MPa. In addition,
with the increase of hydrogen pressure, the yields of THF and 1,4-DAB decreased to a
certain extent. On the contrary, the yield of byproduct BUA decreased along with the
increased hydrogen pressure.
100
98
99
99
96
99
Conv. or Yield / %
80
10
60
33
1a
27
17
34
27
40
20
51
55
53
36
35
2.0
5.0
0.1
0.5
1.0
H2 Pressure / MPa
Figure 3. Effect of hydrogen pressures (relative pressure).
170
1b
1c
Conv.
In addition, discussion on the reaction temperatures was carried out to further
optimize the reaction condition (Table 3). At a reaction temperature of 30 °C, 90% yield
of 1,4-DAB was obtained, and no THF was detected. When the reaction temperature
increased to 100 °C, the production of THF was still not detectable. Moreover, at a
reaction temperature of 170 °C, 60 % yield of THF was achieved. It was discovered
that the hydrogenation of 1,4-DABE could occur around room temperature, and the
hydrolysis and condensation should require a high reaction temperature.
Table 3. Effect of reaction temperatures in the one-pot synthesis of THF from 1,4DABE using Rh/Al-MCM-41.
AcO
OAc
1 mmol
Rh/Al-MCM-41
H2 (0.5 MPa), 24 h
H2O (1 eq.)
1a
AcO
OAc
AcO
1c
1b
Conv.a/% Yield(1a)a/% Yield(1b)a/% Yield(1c)a/%
Entry
Temperature/°C
30
99
n.d.
90
100
92
n.d.
49
19
150
99
55
33
170
98
60
13
13
Determined by GC analysis using tridecane as an internal standard.
Because the hydrogenation reaction was relatively easy to go, compared with the
following hydrolysis and condensation, a discussion was performed to optimize the Rh
loading amount to determine if the loading amount can be reduced to improve the
atomic efficiency and cost of the noble metal (Fig. 4). When the Rh loading amount
was 0.25 wt%, the conversion was relatively low, and a yield of only 18% for THF was
obtained. With the Rh loading amount increasing to 1.0 wt%, the yield of THF increased
up to 55%. Similar results were available when the Rh loading amount was 1.0 wt%
and 2.0 wt%. As the Rh loading amount further increased to 4.0 wt%, decrease in THF
yield was observed. These results reveal that the high yield of THF should be related to
the synergistic effect from Rh NPs and the Al-MCM-41support. The supported Rh NPs
171
not only acted on the hydrogenation process, but also promotes the hydrolysis and
condensation.
100
Conv. or Yield / %
80
>99
99
93
60
14
99
97
11
13
1a
33
1b
27
36
24
1c
Conv.
57
40
46
20
55
55
1.0
2.0
44
18
0.25
0.5
4.0
Rh loading amount / wt%
Figure 4. Discussion on the Rh loading amounts in the one-pot synthesis of THF from
1,4-DABE using Rh/Al-MCM-41.
Furthermore, a NH3-TPD measurement was performed on the Rh/Al-MCM-41
catalysts with various Rh loading amounts to investigate the effect of acid sites in this
reaction (Fig. 5). In the result of reference sample Al-MCM-41, two peaks of NH3
desorption were observed at the weak and strong acid sites. With the loading of Rh NPs,
the NH3 desorption peaks at high temperatures, which were considered strong acid sites,
shifted to higher temperatures, and no obvious changes occurred at low temperatures,
which were considered weak acid sites. This revealed that the loading of Rh NPs
promoted the enhancement of acidity at the strong acid site. However, the great reaction
results of 1 wt% and 2 wt% Rh/Al-MCM-41 and the relative bad reaction results of
0.25 wt%, 0.5 wt% and 4 wt% Rh/Al-MCM-41 further support that an opportune strong
acid site was significant in this reaction.
172
4 wt% Rh/Al-MCM-41
m/z=17 intensity
2 wt% Rh/Al-MCM-41
1 wt% Rh/Al-MCM-41
0.5 wt% Rh/Al-MCM-41
0.25 wt% Rh/Al-MCM-41
Al-MCM-41
50
250
450
Temperature / ºC
650
Figure 5. NH3-TPD profiles of Rh/Al-MCM-41 with different Rh loading amounts
(m/z=17).
7.4. Conclusion
In conclusion, a direct one-pot synthesis method of THF from 1,4-DABE was
developed over bifunctional catalysts Rh0/Al-MCM-41 (Fig. 1b). A maximum yield
around 60% was obtained using the optimized catalysts, and another main product was
1,4-DAB in a yield around 30%, which was an intermediate in the synthesis of THF.
173
The characterization over the catalysts showed that supported Rh NPs were in small
sizes and highly dispersed. In addition, a synergistic effect in the acidity was discovered,
and the loading of Rh NPs enhanced the strong acid sites.
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175
Concluding Remarks
In this doctoral thesis, the author systematically studied the soft Lewis acid
function in supported noble metal nano-catalysts for sustainable synthesis.
In chapter 1, general introduction of the soft Lewis acid catalysis and the
development of supported noble metal catalysts was conducted. It was pointed out that
the sustainable synthesis could be realized by the application of active and stable
heterogeneous catalysts.
In chapter 2, Pt/CeO2 with residual chloride was proved to act as soft Lewis acids
and facilitate the efficient isomerization of allylic esters.
In chapter 3, reusability and deactivation mechanism of this Pt catalysts were
investigated, and a great reactivation method was also developed.
In chapter 4, a facile solvent-free methodology was developed for isomerization
of allylic esters with supported Au NPs catalysts, which showed superior catalytic
activity and stability. Lifetime and stability of the optimized catalyst were evaluated by
a 14-day flow reaction in the scale of kilogram, and no obvious deactivation occurred.
In chapter 5, a sustainable catalytic system for the intramolecular cyclization of
alkynoic acids by using Na-salt-modified Au NPs supported on monoclinic ZrO2 was
realized, and the positive and significant role of the Na salt in this reaction was
disclosed.
In chapter 6, a practical method for regulating and optimizing the activities of
metal-oxide supported Au NP catalysts was well investigated. The catalysts with
smaller specific surface area showed better catalytic activity, and this tread was
obtained in the soft Lewis acid reactions, including isomerization, cyclization, and
hydroamination reactions
In chapter 7, one-pot synthesis of THF was also developed to further enhance the
sustainability of the C4 synthesis process.
These works highlighted that supported noble metal catalysts could be used as
active and stable soft Lewis acid catalyst in multiple valuable reaction, and their
activities could be controlled and optimized, and even be reactivated.
176
Acknowledgment
I would like to express my deepest appreciation to all those who helped me to
complete this thesis. A special gratitude I give to my supervisors, Prof. Makoto
Tokunaga, Associate Prof. Haruno Murayama and Assistant Prof. Eiji Yamamoto who
provided me with the chance to study at Kyushu University and supported me for
carrying out my research smoothly. I also want to acknowledge the help and care from
all the students in Tokunaga Lab.
I would like to thank Dr. Tetsuo Honma for his guidance about XAFS
measurements and result in analysis. I also want to express my thanks to Prof. Mitsutaka
Okumura and Prof. Tamao Ishida for their collaboration on DFT calculation and CODRIFT measurements, respectively. In addition, I want to thank Mitsubishi Chemical
Corporation for the financial support of the research on isomerization reaction.
My gratitude also extends to all the professors, secretaries, and students in the
Advanced Graduate Course on Molecular Systems for Devices.
Finally, I would like to express my gratitude to my family members and my friends
for their kind encouragement and support.
177
List of Publication
[1] Z Zhang, T Mamba, Q.-A Huang, H Murayama, E Yamamoto, T Honma, M
Tokunaga, The Additive Effect of Amines on the Dihydroxylation of Buta-1,3-diene
into Butenediols by Supported Pd Catalyst, Mol. Catal., 2019, 475, 110502.
[2] Q.-A Huang, A Haruta, Y Kumamoto, H Murayama, E Yamamoto, T Honma, M
Okumura, H Nobutou, M Tokunaga, Pt/CeO2 with Residual Chloride as Reusable Soft
Lewis Acid Catalysts: Application to Highly Efficient Isomerization of Allylic Esters,
Appl. Catal. B Environ., 2021, 296, 120333.
[3] Q.-A Huang, T Ikeda, K Haruguchi, S Kawai, E Yamamoto, H Murayama, T Ishida,
T Honma, M Tokunaga, Intramolecular Cyclization of Alkynoic Acid Catalyzed by Nasalt-modified Au Nanoparticles Supported on Metal Oxides, Appl. Catal. A Gen, 2022,
643, 118765.
[4] Q.-A Huang, H Murayama, E Yamamoto, T Honma, M Tokunaga, Investigation of
Reusability and Deactivation Mechanism of Supported Platinum Catalysts in the
Practical Isomerization of Allylic Esters, Catal. Today, 2023, 410, 215–221.
[5] Q.-A Huang, H Murayama, E Yamamoto, A. Nakayama, T Ishida, T. Honma, M
Tokunaga, Engineering Active and Stable Au/ZrO2 Catalysts for Isomerization of
Allylic Esters: A Practical Application of Gold Catalysis, (in preparation)
[6] Q.-A Huang, H Murayama, E Yamamoto, M Tokunaga, Effect of the Structure of
Metal Oxide Support on the Activity of Supported Au Nanoparticles in Soft Lewis Acid
Catalysis, (in preparation)
[7] Q.-A Huang, M. Takaki, H Murayama, E Yamamoto, M Tokunaga, L. X. Dien, T.
Ishida, T. Honma, N. V. Tzouras, T. Scattolin, S. P. Nolan, Supported Gold
178
Nanoparticles
Prepared
from
NHC-Au
Complex
Precursors
as
Reusable
Heterogeneous Catalysts, (in preparation)
[8] Q.-A Huang, H Murayama, E Yamamoto, M Tokunaga, One-pot Synthesis of THF
from But-2-ene-1,4-diyl acetate (1,4-DABE) over Bifunctional Rhodium Silicaalumina Catalysts, (in preparation)
179
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