The effect of heterogeneous acid-base catalysis on conversion of 5-hydroxymethylfurfural into a cyclopentanone derivative

Article abstract of DOI:10.1039/c5gc01723h

The effect of heterogeneous acid-base catalysis on conversion of 5-hydroxymethylfurfural (HMF) to 3-hydroxymethylcyclopentanone (HCPN) was investigated. It was demonstrated that acidic metal oxides, in particular Ta₂O₅, significantly enhanced the yield of HCPN due to their moderate Lewis acidity.

Full text of DOI:10.1039/c5gc01723h

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Effect of Heterogeneous Acid-Base Catalysis on Conversion of 5-
Hydroxymethylfurfural into A Cyclopentanone Derivative
J. Ohyama,a,b* R. Kanao,a Y. Ohira,a and A. Satsumaa,b*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Effect of heterogeneous acid-base catalysis on conversion of 5- compound (e.g., for fragrance), HCPN may be a value-added
hydroxymethylfurfural (HMF) to 3-hydroxymethylcyclopetanone cyclopentanone, because HCPN is -substituted
(HCPN) was investigated. It was demonstrated that the acidic cyclopentanone which is difficult to synthesize from
metal oxides, in particular, Ta2O5, significantly enhanced the yield cyclopentanone although a -substituted cyclopentanone is
a
β
α
of HCPN due to its moderate Lewis acidity.
relatively easily synthesized.21
Several research groups have reported catalytic conversion of
FA to cyclopentanone (CPO) or cyclopentanol (CPL) using
heterogeneous catalysts such as a carbon supported Pt,12, 15
SBA-15 supported Ni-Cu catalysts,16 Cu-Co catalysts,18 and
CuZnAl catalysts.17 Meanwhile, we have reported the
conversion of HMF to 3-hydroxymethylcyclopetanone (HCPN)
using supported Au catalysts.20 The rearrangement of furfural
derivatives is considered to proceed through hydrogenation of
the aldehyde group and the following ring opening and closing
reactions accompanied with hydration and dehydration
(Scheme 1, which is improved from our previously reported
one: In the present study, 3-hydroxymethyl-(2, 3, or 4)-
cyclopentenone (HCPEN) was newly suggested as an
intermediate based on mass spectroscopy). The scheme
suggests that the catalyst system for the ring rearrangement
should have not only hydrogenation activity but also acid-base
catalysis. In the case of the ring rearrangement of FA, it has
been proposed that H2O in a reaction system acts as acid-base
catalyst, and additional acid-base catalysts are not necessary
to obtain CPO.15, 16 On the other hand, our previous study on
the ring rearrangement of HMF using various metal oxides
supported Au catalysts implied that acid-base catalysis of the
metal-oxide-supports contributes to efficient production of
HCPN.20 However, in the previous study, we could not clearly
discuss the effect of acid-base catalysis on the metal oxides on
the ring rearrangement of HMF, since the various supported
Au catalysts did not have an identical hydrogenation activity
due to different sizes and/or chemical states of Au
nanoparticles between the various supported Au catalysts.
In the present study, in order to investigate the effect of acid-
base catalysis on the ring rearrangement of HMF, we
performed the reaction using a combination catalyst system
that is composed of a metal oxide as an acid-base catalyst; Pt
supported on an inert metal oxide (Pt/SiO2) as a hydrogenation
Biorefinery is getting more and more attention for production
of sustainable chemicals and fuels.1,
2
Cellulose and
hemicellulose from woody biomass can be converted to furan
derivatives, 5-hydroxymethylfurfral (HMF) and furfural (FA),
through catalytic reactions including hydrolysis, isomerization,
and dehydration.3, 4, 5, 6 The furan derivatives are regarded as
platform chemicals in the biorefinery process: for example,
hydrogenation and/or hydrogenolysis of HMF produce 2,5-
bis(hydroxymethyl)furan
(BHF),
2,5-
bis(hydroxymethyl)tetrahydrofuran (BHTF), 1,6-hexandiol, and
2,5-dimethylfuran (DMF), which can be utilized for polymers,
fine chemicals, and fuels.5, 7, 8, 9, 10, 11
Very recently, the ring rearrangement of the furan derivatives
has been developed as a new reaction in the biorefinery.2, 12, 13,
14, 15, 16, 17, 18, 19, 20
By the ring rearrangement reaction, HMF and
FA can be transformed to cyclopentanone or its derivatives,
which can be an intermediate chemical for fragrance,
pesticide, polymer, and solvent. In the current petrochemical
process, cyclopentanone and its derivatives have been
produced from adipic acid, which can be produced from
cyclohexanol or cyclohexane.21 In the economic point of view,
the synthesis of cyclopentanone derivatives from HMF and FA
is interesting, since the biomass derived chemicals (HMF, FA)
have potential to be cheaper than the petrochemical (adipic
acid) with depletion of oil resources and with the development
of biorefinery process. In addition, as an intermediate chemical
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catalyst. As the acid-base metal oxides, Ta2O5, ZrO2, Nb2O5, significantly enhanced the HCPN yield (72-82%). It has been
TiO2, Al2O3, and SiO2-Al2O3, CeO2, La2O3, and hydrotalcite were reported that acid facilitates the ring-opening of BHF.27 This is
applied to the reaction. As a result, the acidic metal oxides, in one of the reasons for the relatively high yield of HCPN on the
particular, Ta2O5, enhanced the ring rearrangement of HMF to acidic metal oxides.
HCPN. We also investigated the effective acidity for the
reaction by means of Fourier transformed infrared (FT-IR)
spectroscopy using pyridine as a probe molecule.
Fig. 1. Product distributions obtained by the reaction using Pt/SiO2 with/without
various metal oxides. Reaction condition: HMF aq. (0.067 M, 3 mL); Pt/SiO2 (10 mg); a
metal oxide (10 mg); H2 3 MPa; 140˚C; 12 h. Since HMF was completely converted for
12 h over all catalysts, the yields mean the selectivity.
The pH of the reaction solution with various catalysts was
measured (Fig. S1). The pH of the solution in the presence of
Ta2O5, Nb2O5, TiO2, ZrO2, Al2O3, SiO2-Al2O3, and CeO2 with
Scheme 1. Conversion of HMF to HCPN.
Pt/SiO2 (pH = ca. 4 - 5) did not significantly change from the pH
in the presence of only Pt/SiO2 (pH = ca. 4). When La2O3 and
All of the above metal oxides were calcined at 500˚C before
hydrotalcite were added, the pH (ca. 7-11) increased from that
use. Pt/SiO2 (1 wt% of Pt loading) was prepared by an
of the reaction solution with Pt/SiO2. Although the pH did not
impregnation method using Pt(NH3)4Cl2ꢀ4H2O as a precursor.
significantly change by addition of Ta2O5, Nb2O5, TiO2, ZrO2,
Al2O3, and SiO2-Al2O3, the yield of HCPN largely increased. It
should be also noted that the addition of La2O3 increased the
yield of HCPN (as well as the total yield of the ring rearranged
products (HCPN+HCPEN)) in spite of the increase of the pH. It
is suggested that another factor than the pH (ca. 4 - 8), that is,
the Lewis acid on metal oxide surface, is important for
production of HCPN as discussed later. On the other hand, the
pH in the presence of hydrotalcite was much larger (pH = ca.
11) than that in the presence of Pt/SiO2, and the yield of HCPN
(and the total yield of the ring rearranged products) was
smaller than that in the presence of Pt/SiO2. In addition, the
reaction using hydrotalcite gave 1,2,6-hexanetriol, which can
be produced through total hydrogenation of BHF and following
hydrogenolysis.28 Therefore, the strong basicity of the reaction
solution or the catalyst surface lead the different reaction of
BHF.
Prior to catalytic tests, Pt/SiO2 was pretreated under H2 at
200˚C. Subsequently, Pt/SiO2 was treated under O2 at 200˚C,
since our previous study suggested that the O2 treatment of
supported Pt catalysts is effective for selective hydrogenation
of HMF to BHF.20 The treated Pt/SiO2 (10 mg), a metal oxide
(10 mg), and an aqueous solution of HMF (0.067 M, 3 mL)
were added to an autoclave (30mL, Taiatsu Techno Co., TVS-1
type). The reactor was pressurized with 3 MPa of H2, and the
reaction was carried out at 140˚C.
Fig. 1 exhibits the product distributions obtained by the
reaction using Pt/SiO2 with/without the various metal oxides.
The reaction over any catalysts converted all of HMF, and
provided
hydroxymethyl-(2, 3, or 4)-cyclopentenone (HCPEN), 4-
hydroxy-4-hydroxymethyl-2-cyclopentenone (HHCPEN),
3-hydroxymethylcyclopentanone
(HCPN),
3-
hydroxyl-2,5-hexanedione (HHD), 2,5-bis(hydroxymethyl)furan
(BHF), 1,2,6-hexyanetrial, and undetectable or unidentified bi-
products (possibly humins generated by cross-polymerization
of the reactant and the intermediates.22 The reaction using
only Pt/SiO2 (without metal oxides) produced a low yield of
HCPN (7%). The presence of CeO2, La2O3, and hydrotalcite,
which are basic metal oxides, did not lead a large increase of
the yield of HCPN (less than 25%). On the other hand, the
presence of Ta2O5, ZrO2, Nb2O5, TiO2, Al2O3, and SiO2-Al2O3,
which are known to have acidic character more prominently
than CeO2, La2O3, and hydrotalcite,23, 24, 25, 26 largely increased
the HCPN yield. In particular, Ta2O5, ZrO2, and Nb2O5
For comparison to the results in Fig. 1, the reaction was
performed using Au/Nb2O5 which showed high performance
for HCPN production in our previous work. The HCPN yield on
Au/Nb2O5 was 61%, and smaller than that reported previously
(86%),20 probably owing to the milder condition of the present
work (3 MPa of H2, 140˚C) than the previous one (8 MPa of H2,
160˚C). As a result, the HCPN yields obtained on some of the
present catalysts (Pt/SiO2 + Ta2O5, ZrO2, or Nb2O5) were higher
than that on Au/Nb2O5 (61%). Usually, Pt catalysts have higher
catalytic activity for hydrogenation than Au catalysts. The high
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catalytic activity of Pt catalysts would contribute to the high acidic metal oxides. The yield of HHCPEN reached a peak at 3 h
yield of HCPN in the milder reaction condition of this work. (21%) and then decreased, followed by increase of HCPEN and
Fig. 2(a) shows the time course of the reactant and product HCPN.
yields on the hydrogenation and ring rearrangement reaction In comparison with Pt/SiO2 without addition of metal oxides
using Pt/SiO2 and Ta2O5. In the first 1 h, 77% of HMF was (Fig. 2(b)), Pt/SiO2 with Ta2O5 showed lower yields of HHCPEN
consumed to produce BHF (44% yield), HHCPEN (2%), HCPEN and HHD, and higher yield of HCPEN (Fig. 2(a)). It is suggested
(10%), and HHD (2%). Then, BHF, HHCPEN, and HCPEN were that Ta2O5 facilitates the reaction of HHED to HCPEN and the
consumed to form HCPN. The yield of HHD slightly increased at reaction of HHD to HCPEN, which involve aldol condensation
3 h, and then plateaued. This time course is well consistent and dehydration. As is the case with Ta2O5, the other acidic
with that on Au/Nb2O5 reported previously.20 Accordingly, the metal oxides will facilitate these intermediate steps to give
hydrogenation and ring-rearrangement reaction is considered relatively high yield of HCPN. Without the metal oxides, the
to proceed as Scheme 1: The selective hydrogenation of HMF intermediates (BHF, HHCPEN, and HHD) might be converted to
produces BHF; The furan ring of BHF opens to provide 1- humins,22 although they could not be identified in this study.
hydroxy-3-hexene-2,5-dione
(HHED)
(not
detected, Previously, several research groups have developed ring
represented in parentheses in Scheme1); Intramolecular aldol rearrangement reaction of furfural (FA) to cyclopentanone
reaction of HHED gives HHCPEN; HHCPEN is dehydrated and (CPO).12, 13, 14, 15, 16, 17, 18 In the literature by Hronec et al., the
hydrogenated to produce HCPEN; HCPEN is hydrogenated to conversion of FA to CPO proceeds on Pd supported on carbon,
form HCPN. HCPN is also considered to be produced through although carbon is usually less active or inert as an acid
HHD formed by hydrogenation of HHED: intramolecular aldol catalyst compared to the acidic metal oxides used in this
condensation of HHD and the following hydrogenation study.12, 15 Yang et al. demonstrated that the reaction of FA to
produce HCPN. In the reaction scheme, Pt/SiO2 facilitates the CPO requires H2, H2O, and a catalyst for hydrogenation (Ni-Cu
hydrogenation reaction, and Ta2O5 is considered to facilitate bimetallic catalyst supported on SBA-15 in their study); the
the steps involving acid-base catalysis, which are hydration, addition of acid-base catalysts does not increase the yield of
aldol reaction, and dehydration.
CPO.16 It has been proposed that H2O in the reaction system
works as an acid catalyst in the conversion of FA to CPO.15,16
Yang et al. also presented that the effective catalytic system
for the conversion of FA to CPO does not work for the
conversion of HMF to HCPN. On the other hand, we
demonstrated that acid catalysts are necessary to obtain high
yield of HCPN by facilitating the dehydration process. It is
possible that the activation energies for aldol condensation
and dehydration (HHED to HCPEN and HHD to HCPEN) are
much larger than the corresponding activation energies for the
ring rearrangement of FA. The acidic metal oxides will reduce
the activation energies of those processes for HCPN
production by their acid catalysis.
To investigate the effective acid for the production of HCPN,
the acid type and strength of metal oxides was evaluated from
the FT-IR spectra of pyridine adsorbed on the metal oxides
shown in Fig. 3. All of the spectra showed bands at around
1445 cm-1 and 1610 cm-1 assignable to the
ν19b and ν8a mode of
pyridine adsorbed on Lewis acid site. The FT-IR spectrum of
SiO2-Al2O3 also exhibited a small band assignable to the ring
stretching ν19b mode of pyridine adsorbed on Brønsted acid
site at around 1545 cm-1, but the other metal oxides showed
almost no band at around 1545 cm-1. Since SiO2-Al2O3 gave
lower yield of HCPN than the other acidic metal oxides, the
Lewis acid is considered to be responsible for the production
of HCPN. It should be also noted that CeO2, La2O3, and
hydrotalcite showed the pyridine adsorbed on the Lewis acid
sites. The presence of Lewis acid sites on the basic oxides can
explain their production of HCPN, HCPEN, and HHD (Fig. 1).
Fig. 2. Time courses of the conversion of HMF and the yields of the products on the ring
rearrangement reaction using (a) Ta2O5 and Pt/SiO2 and (b) only Pt/SiO2. The
conversions and yields are averages of two experiments (Figs. S2 and S3). The error
bars indicate the difference between the two experiments.
The time course of HMF conversion and the product yields on
Pt/SiO2 was also examined for comparison. As shown in Fig.
2(b), HMF was converted to BHF, HHCPEN, HCPEN, and HHD in
the first 1 h. It should be noted that the ring-opened and
rearranged products were produced in the reaction without
the acidic metal oxides. This result suggests that the ring
opening and closing reactions proceeds in the absence of the
The peak wavenumber of pyridine (ν8a) adsorbed on Lewis
acid sites at around 1610 cm-1 increased in the order of La2O3 <
hydrotalcite < CeO2 < TiO2 < Nb2O5 ≈ ZrO2 < Ta2O5 < Al2O3 <
SiO2-Al2O3. The higher wavenumber suggests stronger Lewis
acid of metal oxides.25, 29 To inspect the effect of Lewis acid
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strength on the production of HCPN, the HCPN yields (Fig. 1) This work was supported by Grant-in-Aids from the Ministry of
were plotted against the peak wavenumbers of adsorbed Education, Culture, Sports, Science and Technology (MEXT),
pyridine (ν8a) as shown in Fig. 4. The plot showed a volcano Japan – Young Scientists (B) (No. 25820393).
shape, which indicates Lewis acid with moderate strength led
to high yield of HCPN. Based on the above results, it is
reasonable to conclude that metal oxides with moderate Lewis
acidity are effective for the aldol condensation and
dehydration for the ring rearrangement reaction, and enhance
the yield of HCPN.
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1
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Acknowledgements
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Acidic metal oxides, in particular, Ta2O5, significantly enhanced the conversion of 5-hydroxymethylfurfral to
a cyclopentanone derivative.
161x119mm (150 x 150 DPI)