Synthesis of formic acid from monosaccharides using calcined Mg-Al hydrotalcite as reusable catalyst in the presence of aqueous hydrogen peroxide

Article abstract of DOI:10.1021/op5004083

Formic acid (FA) can be synthesized from monosaccharides such as glucose, galactose, xylose, arabinose and lyxose by using both calcined Mg-Al hydrotalcite as a solid catalyst and aqueous H₂O₂ as an oxidant in ethanol solvent at 343 K for 5 h. For the glucose oxidation, the FA yield and H₂O₂ utilization efficiency reach 78% and 100%, respectively. The used hydrotalcite catalyst can be easily separated from the reaction mixture and is reusable at least twice.

Full text of DOI:10.1021/op5004083

Article
pubs.acs.org/OPRD
Synthesis of Formic Acid from Monosaccharides Using Calcined Mg-
Al Hydrotalcite as Reusable Catalyst in the Presence of Aqueous
Hydrogen Peroxide
Ryo Sato, Hemant Choudhary, Shun Nishimura, and Kohki Ebitani*
School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1, Asahidai, Nomi, Ishikawa 923-1292, Japan
S
* Supporting Information
ABSTRACT: Formic acid (FA) can be synthesized from monosaccharides such as glucose, galactose, xylose, arabinose and
lyxose by using both calcined Mg-Al hydrotalcite as a solid catalyst and aqueous H2O2 as an oxidant in ethanol solvent at 343 K
for 5 h. For the glucose oxidation, the FA yield and H2O2 utilization efficiency reach 78% and 100%, respectively. The used
hydrotalcite catalyst can be easily separated from the reaction mixture and is reusable at least twice.
65−70% yields (12 h).27 In continuation of our work, we
INTRODUCTION
■
hereby demonstrate the FA synthesis from various mono-
Formic acid (HCOOH, FA) has attracted much attention as a
saccharides using calcined Mg-Al hydrotalcite35−42 as a simple
hydrogen storage organic molecule because FA can be
converted into H2 and CO2 using catalysts.1−6 FA is a stable
and reusable catalyst in the presence of aq H2O2 in ethanol
solvent at 343 K with an excellent H2O2 utilization efficiency
liquid at room temperature (bp 374 K) and is nontoxic and
nonflammable, which enables easy handling, and it can be used
(Scheme 1).
for various reductive transformations of organic compounds as
a hydrogen source.7−13
Scheme 1. Synthesis of Formic Acid (FA) by Oxidation of
Glucose Using Calcined Mg-Al Hydrotalcite Catalyst in the
Presence of Aqueous H2O2 in Ethanol Solvent
The fermentations of saccharides are the key process for FA
synthesis;14 however, they are expensive because of product
purification and strict control of reaction conditions (pH and
temperature). Industrially, FA has been produced from a
CH3ONa-mediated carbonylation of CH3OH under pressur-
ized CO (40 MPa) to form methyl formate, followed by its
hydrolysis with excess water.15 It has also been reported that FA
can be obtained from H2 and CO2 using homogeneous metal
catalysts under pressurized conditions (4−18 MPa).16−20
Utilization of biomass-based materials as a renewable
resource of valuable chemicals such as fuel and polymer has
been extensively reported using solid catalysts.21−26 Accord-
ingly, the biomass-based FA productions from cellulosic
biomass such as saccharides (sugars or carbohydrates) are
attractive systems,27−34 which will open up the way to an
indirect utilization of solar energy via plants.
EXPERIMENTAL SECTION
■
Hydrotalcite (HT, Mg/Al = 5.4) was supplied from Tomita
Phamaceutical Co. Ltd. as AD500PF (particle size; 6.4 μm, and
surface area; 57 m2 g−1). The layered structure was confirmed
by a powder XRD measurement. D-Glucose, FA, aq H2O2, CaO
and γ-Al2O3 were supplied from Wako Pure Chem Co. Ltd.. D-
Fructose, D-xylose, D-galactose, dehydrated ethanol, N,N-
dimethylformamide (DMF), MgO, ZrO2 and TiO2 were
purchased from Kanto Chem. Co. Inc.. The Catalyst Society
of Japan supplied proton-forms of ZSM-5 (Si/Al = 45, JRC-Z5-
90H) and β-type (Si/Al = 12.5, JRC-Z-Hβ 25) zeolites. D-
Arabinose and D-lyxose were supplied from Acros Organics and
Tokyo Chemical Ind. Co. Ltd., respectively. SiO2, SrO,
Amberlyst-15 and Amberlyst-A26(OH) were purchased from
Sigma-Aldrich Co. Ltd..
In 1974, Isbel and Naves communicated formation of FA
using alkaline hydrogen peroxide from saccharides via an
oxidation mechanism by OOH− species.33 A research group of
Enomoto has strikingly reported the FA synthesis from
carbohydrates under hydrothermal conditions at 523 K in the
presence of concentrated H2O2 and NaOH, where the
maximum FA yield was 70%.29,31 Wolfel et al. demonstrated
̈
the oxidation of saccharides with pressurized O2 (3 MPa) at
353 K for 26 h in water using a Keggin-type polyoxometalate
catalyst, H5PV2Mo10O40·35H2O, to yield ca. 50% FA.30 An
acidic Amberlyst-70 could convert cellulose to FA with 53%
yield in water at 453 K for 50 h under 0.3 MPa of Ar.28
Recently, we reported the conversions of glucose or xylose
using CuOx/MgO catalyst, hydrothermally prepared with
cetyltrimethylammonium bromide as a capping agent, in the
presence of aqueous (aq) H2O2 at 393 K, which gives FA with
In a typical reaction procedure, glucose (0.56 mmol) was
weighed in a 50 mL Schlenk tube, followed by the addition of
calcined HT (0.1 g). The HT was calcined in air at 723 K for 5
h at a ramp rate of 10 K min−1, which converts the layered
structure of HT into well mixed Mg-Al oxides possessing an
Received: December 24, 2014
© XXXX American Chemical Society
A
DOI: 10.1021/op5004083
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Article
acid−base bifunctional surface.42 Thereafter, ethanol (5 mL)
and aq H2O2 (2.8 mmol) were added in the Schlenk tube and a
N2 flow was maintained. The solution was stirred at 343 K for 5
h to achieve a high glucose conversion. After the reaction, the
reactants were allowed to cool down to room temperature for
20 min. The resultant reaction mixture was diluted to 20 times
with water, and the catalyst was filtered off using a Milex
syringe filter (0.20 μm). The obtained filtrate was analyzed by
high performance liquid chromatography (HPLC, WATERS
600) using an Aminex HPX-87H column (Bio-Rad Lab. Inc.)
attached to a refractive index detector. Aq H2SO4 (10 mM) at a
flow rate of 0.5 mL min−1 was run through the column
maintained at 323 K. A 20 μL sampling loop was used for
injection. A HPLC chromatogram is shown in Figure S1. The
conversion, yield and selectivity were calculated using the
equations as shown below:
The catalytic activities of various solid catalysts for the
glucose oxidation using water as a solvent are shown in Table 1.
Table 1. Oxidation of Glucose over Various Solid Catalysts
a
in Water Solvent.
FA
Entry
Catalyst
HT
Conv/%
Yield/%
Selectivity/%
1
2
3
4
5
6
7
8
9
50.1
51.5
74.9
63.8
94.7
<0.1
7.8
23.1
29.6
37.3
13.8
25.8
-
46.1
57.5
49.9
21.6
27.2
-
b
Calcined HT
MgO
H-ZSM-5
H-β zeolite
%Conversion = Amount of substrate used (mmol)
[
Amberlyst-15
γ-Al2O3
SiO2
− Amount of substrate after
-
-
13.2
<0.1
-
-
reaction (mmol)
]
ZrO2
-
-
a
/ Amount of substrate used (mmol)
[
]
Reaction conditions: glucose (0.56 mmol), catalyst (0.10 g), water
(2.75 mL), 25% H2O2 (2.8 mmol), 363 K, 5 h, N2 atmosphere.
× 100
b
Calcined at 723 K in air.
%Yield = Number of carbons in product × Amount of
[
Use of the calcined Mg-Al HT afforded FA with 29.6% yield
and 57.5% selectivity at 51.5% glucose conversion (entry 2).
Under the same reaction conditions, uncalcined HT and MgO
also produced FA; however, the selectivity was less than 50%
(entries 1 and 3). Solid acid catalysts such as H-ZSM-5 and H-β
zeolites demonstrated lower selectivities for FA (entries 4−5).
FA cannot be obtained from the reaction with some other solid
acid catalysts, such as Amberyst-15, Al2O3, SiO2 and ZrO2
(entries 6−9). From these results, the calcined-HT afforded the
highest selectivity for FA from glucose, and therefore, we
decided to conduct the glucose oxidation using calcined-HTs as
catalysts.
Screening of solvent with the calcined-HT catalyst revealed
that lower alcohols are suitable for selective synthesis of FA.
The FA yields (selectivities) in various solvents at 343 K are as
follows: 1-butanol 58% (61%), 1-propanol 53% (62%), ethanol
55% (65%), methanol 54% (65%), water 29% (38%), and DMF
13% (18%). Considering greener aspects and safety of
operations, ethanol was chosen as a solvent for further
experiments.
In ethanol solvent, the catalytic activities of various catalysts
were also examined. For the reaction in ethanol solvent, the
glucose oxidation did not occur without catalyst nor aq H2O2
(Table 2, entries 1 and 5). During the optimization of the
catalytic activity with calcined HT in ethanol, we realized an
increase in the FA yields with the increase in amount of aq
H2O2 and a maximum FA yield was achieve with 5 mmol of aq
H2O2 (entry 4). A necessity of calcination of the Mg-Al HT was
also confirmed since the parent HT failed to produce any FA
(entry 2 vs entry 3). Even without calcination, the original Mg-
Al HT has basic sites which can work in an aqueous
media41,44,45 (also see Table 1, entry 1) and a change of
color of brilliant cresyl blue (pKa = 11) to a basic color could be
observed.46,47 These basic sites are able to generate OOH−
species from H2O2, which oxidizes olefins into the correspond-
ing epoxides.36,39 In this work, it was observed that parent HT
failed to yield FA from glucose in ethanol solvent. These results
product formed (mmol)
]
/ Number of carbons in substrate × Amount of
[
substrate used (mmol) × 100
]
Yield
Conversion
%Selectivity =
× 100
Recycling experiments were carried out to establish the
applicability of the catalyst in the glucose oxidation to FA. After
a catalytic run, the reaction mixture was transferred to a
centrifugation tube, and the reactor was washed using water to
make up volume to 9 mL, followed by centrifugation to decant
the supernatant liquid (after a part of the liquid was kept for
HPLC analysis). Acetone was added to the left over solid
residue and sonicated for a few minutes. The process was
repeated three to five times, and the obtained catalyst was dried
under vacuum overnight. The dried catalyst was grained and
calcined in air at 723 K for 5 h at a ramp rate of 10 K min−1.
Thus, obtained catalyst was used for recycle experiments
following the method as described above.
An actual concentration of H2O2, determined by an
iodometric titration method,43 was found to be 25.4%.
RESULTS AND DISCUSSION
■
Preliminary experiments for the glucose oxidation in water
solvent demonstrated that at 363 K the main product was FA
with formation of glycolic acid (GA; a C2 carboxylic acid) as a
byproduct (Figure 1), which is formed by an oxidative C−C
bond cleavage of glucose. At present, we do not consider GA as
an intermediate for FA because of its low reactivity (vide infra).
Figure 1. Structure of glycolic acid (GA).
B
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Organic Process Research & Development
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assuming that one mole of glucose produces 6 mol of FA
according to the following equation.29
Table 2. Effect of Catalyst on FA Selectivity in the Glucose
Oxidation Using Aqueous H2O2
a
C6H12O6 + 6H2O2 → 6HCOOH + 6H2O
Yield/%
Selectivity to
It should be noted that the H2O2 utilization efficiency in this
work was almost 100%; 2.5 mmol of H2O2 was consumed after
the reaction, producing 0.44 mmol of FA. Theoretically, 2.62
mmol of H2O2 (=0.44 mmol of FA × 6) should be consumed
in this glucose oxidation.54
Entry
Catalyst
Conv/%
FA
GA
FA/%
1
2
3
-
4.8
24.7
86.4
>99
-
-
-
-
Uncalcined HT
-
-
b
HT
54.4
78.1
-
3.7
1.7
15.0
1.7
2.6
1.3
0.9
-
63.0
78.1
-
c
b
4
d
HT
Recyclability of the catalyst is also a key criterion in solid-
b
catalyzed organic reactions.55 As shown in Figure 2, the
5
HT
24.1
36.0
46.6
95.6
50.5
43.5
30.7
25.3
58.9
13.0
61.5
6
Uncalcined MgO
2.9
21.3
29.8
4.2
2.1
0.3
-
8.1
45.8
31.2
8.4
4.8
0.9
-
b
7
MgO
b
8
SrO
b
9
CaO
10
11
12
13
14
15
Amberlyst-15
Amberlyst-A26(OH)
-
b
γ-Al2O3
-
Uncalcined H-ZSM-5
4.9
0.8
2.4
1.2
-
8.3
0.9
3.9
b
H-ZSM-5
Uncalicned
0.5
H-β zeolite
b
16
17
H-β zeolite
9.0
-
-
-
-
-
-
b
SiO2
11.0
a
Reaction conditions: glucose (0.56 mmol), catalyst (0.10 g), ethanol
(2.75 mL), 25% H2O2 (2.8 mmol), 343 K, 5 h, N2 atmosphere.
Calcined at 723 K for 5 h in air. 25% H2O2 (5 mmol). Without aq
b
c
d
Figure 2. Reusability of calcined HT catalyst for the oxidation of
glucose using aq H2O2. Blue and red bars are the conversion of glucose
and the yield of FA, respectively. Reaction conditions: glucose (0.56
mmol), calcined Mg-Al HT (0.10 g), ethanol (2.75 mL), 25% H2O2
(2.8 mmol), 343 K, 5 h, N2 atmosphere. The numbers indicate the
conversion and yield of glucose and FA, respectively.
H2O2.
suggest that the formation of OOH− species by parent HT and
H2O2 was inhibited in the presence of ethanol, which is
necessary for the FA production33 (vide infra) (entry 2).
Like uncalcined HT catalyst, the uncalcined MgO also
demonstrated lower activities for FA formation in ethanol
(Table 2, entry 6). Calcination of MgO, SrO and CaO could
convert glucose; however, the FA selectivities were low (entries
7−9) compared to that for the calcined-HT due to their strong
basicities.44,45 Large differences between glucose conversions
and product yields imply an occurrence of side-reactions.48 The
Amberlyst-15, which has SO3H moieties as Bronsted acidic sites
(H0: −2.2),49−52 is not able to produce FA (entry 10). The
Amberlyst-A26(OH), known as a strong basic material which
contains quaternary ammonium groups,53 is also incapable of
oxidizing glucose to FA (entry 11). Although uncalcined H-
ZSM-5 and H-β zeolite catalysts showed activities for FA
production in water, the reaction over them failed to progress
in ethanol (Table 2, entries 13 and 15). Furthermore, FA
cannot be obtained over calcined Al2O3, H-ZSM-5, H-β zeolite,
and SiO2 (entries 12, 14, 16, and 17) in ethanol.
The acid catalysts (such as Amberlyst-15 or H-ZSM-5)
demonstrated low or no selectivity for FA. In addition, the
calcination of solid base catalysts afforded FA under our
reaction conditions. Calcination of HT (also see Figure S2)
produces Mg-Al mixed oxide with an acid−base bifunctional
surface;42 it is, therefore, suggested that the acid−base pair with
a moderate strength on the surface play a pivotal role for the
high yield (selectivity) of FA from glucose using aq H2O2 in
ethanol. The oxygen atoms of glucose molecule might
coordinate on the acid sites of calcined HT catalyst, which
would react with the OOH− species generated from H2O2 on
the neighboring base sites.
calcined Mg-Al HT catalyst is reusable at least twice without
losing the high activity and selectivity to FA. The initial kinetics
of the reaction for the fresh and spent catalyst were also
observed as the similar rate between them (Figure S3). After
the reaction, the mixed Mg-Al oxide structure of the calcined
HT could be transformed to the layered HT structure with
water (memory effect35) and lose its activity. In recycling
experiments, therefore, the used HT catalyst was washed with
acetone and dried at room temperature under a vacuum,
followed by calcination at 773 K prior to the further reactions.
Also, the X-ray diffraction (XRD) patterns of the catalyst before
the catalytic run (calcined hydrotalcite) can be observed again
after the calcination of the used catalyst (see Figure S2).
Viability of this catalytic system has been evaluated for the
oxidation of various monosaccharides including pentoses into
FA in the presence of aq H2O2 (5 mmol). As shown in Figure
3, we successfully found that various monosaccharides,
including fructose, galactose, xylose, arabinose and lyxose,
could be transformed to FA in good yields (>70%) with 100%
saccharide conversion. In the case of fructose, however, the
oxidation was not selective; GA was also formed considerably.
A keto group at the second carbon in fructose may facilitate a
cleavage of the bond between the second and third carbons,
which resulted in GA formation (see Scheme S1 for the GA
formation mechanism).
According to Isbel and Naves,33 it was expected that
oxidation of aldohexose would begin with the addition of
OOH− species to the aldehydic carbon atom of the acyclic form
of the aldohexose (Scheme S2), followed by decomposition to
the next lower aldohexose and formic acid (Scheme 2).
The H2O2 utilization efficiency is an important assessment in
oxidation reactions using H2O2 as an oxidant. We calculated the
H2O2 utilization efficiency based on a titration method,
C
DOI: 10.1021/op5004083
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ASSOCIATED CONTENT
* Supporting Information
HPLC chromatogram, XRD, acyclic forms of saccharides, and
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DOI: 10.1021/op5004083
Org. Process Res. Dev. XXXX, XXX, XXX−XXX