Glucose Isomerization Using Alkali Metal and Alkaline Earth Metal Titanates

Article abstract of DOI:10.1002/cctc.201700068

Glucose isomerization was performed using various titanate catalysts, which include SrTiO₃, BaTiO₃, CaTiO₃, Na₂Ti₆O₁₃, K₂Ti₆O₁₃, and Sr₃Ti₂O₇, prepared using a conventional solid-phase method. Among the titanates, SrTiO₃, CaTiO₃, and Na₂Ti₆O₁₃ offered a relatively high fructose yield (32 %) with a high selectivity (68–78 %). The yields are comparable to yields reported previously using a Sn-modified BEA zeolite, which shows a high efficiency for glucose isomerization as a Lewis acid catalyst. A study of the mechanism of glucose isomerization on a SrTiO₃ catalyst surface by using ¹H NMR spectroscopy suggested that the titanates catalyze the isomerization as base catalysts. Thus, the effect of the basicity of the titanates on glucose isomerization was investigated in terms of the base quantity and strength. The analysis was performed by using an acid–base titration method and FTIR spectroscopy with CHCl₃ as a probe molecule. It is proposed that glucose isomerization on the titanates depends not only on the base amount but also on the base strength.

Full text of DOI:10.1002/cctc.201700068

Accepted Article
Title: Glucose Isomerization Using Alkaline and Alkaline Earth
Titanates
Authors: Junya Ohyama, Yutong Zhang, Jun Ito, and Atsushi Satsuma
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Glucose Isomerization Using Alkaline and Alkaline Earth
Titanates
[
a, b]
[a]
[a]
[a, b]
Junya Ohyama,*
Yutong Zhang, Jun Ito, Atsushi Satsuma*
[
9, 11]
Abstract: Glucose isomerization was performed using various
titanate catalysts, including SrTiO , BaTiO , CaTiO , Na Ti
Ti 13, and Sr Ti , prepared using a conventional solid phase
method. Among the titanates, SrTiO , CaTiO , and Na Ti 13 offered
basicity.
isomerization.
Heterogeneous Lewis acids also catalyze the
[
1, 7, 12-14]
3
3
3
2
6 13
O ,
Among acid-base catalysts for glucose
K
2
6
O
3
O
2 7
isomerization reported so far, a tin-modified BEA zeolite, which
functions as a Lewis acid catalyst, exhibits high efficiency for the
isomerization reaction in aqueous media (32% fructose yield).
Alkaline and alkaline earth metal titanates as catalyst
materials have been extensively studied, particularly due to their
3
3
2
6
O
[
1]
a relatively high fructose yield (32%) with high selectivity (68–78%).
The yields are comparable to previously reported yields using a tin-
modified BEA zeolite, which shows high efficiency for glucose
isomerization as a Lewis acid catalyst. A study of the mechanism of
high photocatalytic activity for water splitting, CO
2
reduction, CH
4
1
[15-19]
glucose isomerization on a SrTiO
3
catalyst surface using H-NMR
reforming, etc.
catalysts in the oxidation of hydrocarbons.
They are also utilized as supports of metal
[
20-21]
spectroscopy suggested that the titanates catalyze the isomerization
as base catalysts. Thus, the effects of basicity of the titanates on
glucose isomerization were investigated in terms of base quantities
and strength of the titanates. The analysis was performed by an
It is expected
that the acid-base properties of the titanates would contribute to
their unique catalytic activity through adsorption of reactants and
products. However, there are only a few reports on their acid-
acid-base titration method and FT-IR spectroscopy using CHCl
3
as a
base property. Acidity of SrTiO
perovskite structure, has been investigated using chemisorption
of pyridine and CO adsorption, followed by Raman and infrared
(IR) spectroscopy, and CO temperature programed desorption
The data indicated that the perovskite type titanates
3 3
and BaTiO , which have a
probe molecule. It is proposed that glucose isomerization on the
titanates is dependent not only on the base amounts, but also on the
base strength.
2
2
[
21-23]
(
TPD).
have basicity and weak Lewis acidity. In addition, acid-base
properties of the perovskite type titanates can be controlled by
Introduction
[24]
the counter cations.
The controllable acid-base property is
expected to be useful towards tailoring finely tuned acid-base
Glucose isomerization has generated renewed interest because
it is an intermediate step in biorefinery processes that convert
catalysts. However, to our knowledge, titanates have been rarely
[24]
applied to acid-base reactions.
On the other hand, various
[1-5]
cellulose to fuels and chemicals.
Currently, glucose/xylose
metallates have been developed as acid-base catalysts. One of
isomerase is used for the isomerization of glucose to fructose in
the food industry (42% fructose yield at 60 °C), e.g., production
the most extensively studied metallates is heteropoly
[25-27]
compounds.
Variation of counter cations for heteropoly acid
[
1, 6]
of high fructose syrup.
However, the enzymatic process is
tunes the acidity, and promotes efficient catalytic reactions. For
example, one of the authors of this paper reported that the
variation of counter cations for a heteropoly acid enhanced
hydrolysis of cellulose and Friedel–Crafts acylation and
expensive due to the strict control of reaction conditions. Thus,
highly active, robust, and cheap inorganic catalysts are
[
1]
required. A homogeneous base such as sodium hydrate is
known to catalyze the isomerization of glucose, but often offers
[28-29]
alkylation.
a
low yield of fructose (< 10%) due to degradation of
Herein, we applied various alkaline and alkaline earth
titanates as acid-base catalysts in glucose isomerization. The
acid-base properties of titanates, used as catalysts for glucose
isomerization, were analyzed using proton nuclear magnetic
[1, 7-8]
monosaccharides into byproducts.
Compared to
a
homogeneous base, relatively higher yields of fructose can be
[
9-11]
obtained using a heterogeneous base.
been reported that hydrotalcite offers fructose in 25% yield.
Metallosilicates as base catalysts also offer high fructose yields
For example, it has
[
9]
1
resonance ( H-NMR) spectroscopy, acid-base titration, and
Fourier transform infrared (FT-IR) spectroscopy.
[10-11]
(
20–40% yield of fructose).
Interestingly, the catalytic
performance of hydrotalcite and metallosilicate in the
isomerization reaction was improved through control of their
Results and Discussion
Figure 1 shows the XRD patterns of the prepared titanates. The
[
[
a]
b]
Dr. J. Ohyama, Ms. Y. Zhang, Mr. J. Ito, Prof. A. Satsuma
Graduate School of Engineering
Nagoya University
Furo-cho,Chikusa-ku, Nagoya 464-8603, Japan
E-mail: ohyama@apchem.nagoya-u.ac.jp (J.O.)
satsuma@apchem.nagoya-u.ac.jp (A.S.)
Dr. J. Ohyama, Prof. A. Satsuma
Elements Strategy Initiative for Catalysts and Batteries (ESICB)
Kyoto University
XRD data confirms that SrTiO
perovskite structures (PDF2 nos. 01-080-1935, 01-079-2264,
and 01-070-8503), and Na Ti Ti 13, and Sr Ti have
3 3 3
, BaTiO , and CaTiO have
2
6
O13, K
2
6
O
3
2 7
O
perovskite-like structures (PDF2 nos. 01-073-1398, 01-074-0275,
and 01-076-0740). The specific surface areas of the titanates
2
−1
determined by N
2
adsorption were 1.8-5.6 m g . The structures
and surface areas of the samples are listed in Table 1.
Katsura, Kyoto 615-8520, Japan
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ChemCatChem
10.1002/cctc.201700068
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(
32%). Among the three titanates, SrTiO
selectivity for fructose (78%). The fructose yield and selectivity
for SrTiO is superior to that of TiO and SrCO , which are the
precursors of SrTiO (Table 1, entries 7 and 8). Thus, the
titanate structure improves the performance of glucose
isomerization. The reaction performance of SrTiO was also
better than La and hydrotalcite, which are conventional base
catalysts (Table 1, entries 9 and 10). In addition, the fructose
yield and selectivity using SrTiO was comparable to that of a
3
showed the highest
3
2
3
3
3
2
O
3
3
tin-modified BEA zeolite, a Lewis acid catalyst used in a
previous report (32% fructose yield with 71% selectivity by 45%
[
1]
glucose conversion).
To examine the heterogeneous catalysis of SrTiO
leaching test was performed. Figure 2 shows the time course of
glucose conversion using SrTiO , with and without the removal
of SrTiO in the middle of the reaction. As presented in Figure
(a), an increase in glucose conversion stopped at 15 min when
3
, a
3
3
2
SrTiO
3
was removed by centrifugation, although glucose
conversion continued to increase for 30 min without the removal
SrTiO This indicates that SrTiO catalyzes the glucose
isomerization as a heterogeneous catalyst. The reaction solution
using SrTiO was analyzed using ICP and 0.033 mmol of Sr was
detected in the reaction solution. The leaching of Sr was much
less than the total amount of Sr in SrTiO used as catalyst (ca.
%). Sugar derived acids as byproducts might be responsible for
3
.
3
3
Figure 1. XRD of the titanates prepared in this study.
3
3
[
8]
the leaching. Based on the above results, it is reasonable to
assume that the titanates function as heterogeneous catalysts
for the glucose isomerization, but their alkaline or alkaline earth
metal components partly (probably from surfaces of the
titanates) leach out from the reaction solution.
The results of glucose isomerization using the alkaline and
alkaline earth titanates are presented in Table 1. Fructose and
mannose were obtained as products of the isomerization
[
8]
reaction. The other products are likely sugar derived acids.
comparison between the various titanates shows that SrTiO
CaTiO , and Na Ti 13 offer relatively high yields of fructose
A
3
,
3
2
6
O
Table 1. Results of glucose isomerization, specific surface areas, and base amounts of catalysts.
[
a]
Results of glucose isomerization (%)
[b]
[c]
S
m
BET
Base amount
−1
Entry
Catalyst
−1
(
2
g
)
(mmol g )
Glucose cov.
Fructose yield
Mannose yield
Fructose selc.
1
2
3
4
5
6
7
8
9
SrTiO
3
41
33
47
45
23
60
8
32
23
32
32
17
34
6
5
3
78
70
68
71
74
57
75
47
26
44
78
5.3
4.8
3.4
1.8
5.6
5.0
79.5
-
0.15
BaTiO
3
0
CaTiO
Na Ti
3
8
0.075
2
6
O
13
7
0.175
K
2
Ti
Ti
TiO
SrCO
6
O
13
-
0.025
Sr
3
2
O
7
10
-
1.2
2
-
-
-
-
-
3
17
77
41
32
8
-
Hydrotalcite
La
Recycled
20
18
25
10
17
4
18.1
7.0
-
1
0
1
2 3
O
1
[
a] Reaction conditions: 2 mL of 10wt% glucose aq.; 0.2 g of catalyst; 110 °C, 1 h. [b] Specific surface areas were determined using the BET method. [c]
Determined using an acid-base titration method using phenolphthalein as an indicator.
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3
Figure 2. The time course of glucose conversion using SrTiO : (a) removal of
SrTiO at 15 min (red circle); (b) without the removal (black square).
3
To evaluate the reusability of the catalyst, SrTiO
recycled by filtration after 1 h of the first reaction, and then dried
at 80 °C. The recycled SrTiO exhibited lower glucose
conversion and fructose yield compared to the fresh SrTiO (c.f.
Table 1, entries 1 and 11). Thus, SrTiO does not have high
reusability, which might be related to the leaching of Sr from
SrTiO surface. Suppression of the leaching and improvement in
reusability are challenges to be addressed in the future.
3
was
3
3
3
3
[
7]
Davis et al.
evaluated the mechanism of glucose
isomerization using NMR analyses of reaction solutions of
deuterated glucose at C-2 position. The glucose isomerization is
catalyzed by a base and a Lewis acid, which follow different
[
7]
reaction mechanism as presented in Scheme 1. When using
Lewis acid catalysts, the glucose isomerization proceeds via
intramolecular hydride shifts from C-2 position to C-1 position as
glucose-D2 is transformed to fructose-D1. On the other hand,
when using base catalysts, such as NaOH, proton transfer from
glucose C-2 position to base catalysts causes the isomerization.
Scheme 1. Mechanism of glucose isomerization catalyzed by (a) base and (b)
Lewis acid (B: Base, L: Lewis acid).
[7]
In the case of glucose-D2 isomerization in H
abstracted glucose-D2 abstracts a proton from H
since H O is a larger proton source than deuterons generated
2
O, the deuteron-
2
O solvent,
2
Based on the above NMR analyses, basicity of the alkaline
and alkaline earth titanates is assumed to affect the efficiency of
glucose isomerization. Thus, we investigated the effect of
basicity of the titanates on the glucose isomerization reaction.
Base amounts of the titanates were evaluated using a titration
method with phenolphthalein as an indicator. In Figure 4, the
glucose conversion and the fructose yields on the titanates
from glucose-D2. It should be also noted that the reverse
isomerization of fructose to glucose via the proton transfer
mechanism yields non-D-labeled glucose from glucose-D2.
Figure 3 shows a NMR spectrum of glucose-D2, reacted with
SrTiO
NaOH aq., glucose-D2, and unlabeled glucose as references.
The reacted glucose-D2 with SrTiO showed resonances arising
from a proton in the C-2 position of unlabeled glucose at  =
.25 ppm (Figure 3(a)), which also appear in the spectrum of
glucose-D2 reacted in 2.5 mM NaOH aq. (Figure 3(b)). This
indicates that SrTiO functions as a base catalyst in the
isomerization reaction.
3 2
in H O, along with spectra of glucose-D2 reacted in
3
(
Table 1, entries 1–6) are plotted against their base amounts.
Both glucose conversion and fructose yield tend to increase with
the base amount. Effect of base amounts on fructose selectivity
was also investigated. The fructose selectivity was evaluated at
3
3
4
0–50% glucose conversion by modifying catalyst amounts
and/or reaction time in the case of the reaction using BaTiO and
Sr Ti . Figure 5 presents the fructose selectivity as a function
3
3
2 7
O
of the base amount used for the reaction. The fructose
selectivity increases with the base amount from 0.075 to 0.175
mmol, and then decreases slightly. The effect of the base
amounts on glucose isomerization is similar to the effect of pH
[
8]
reported by Tessonnier et al. using various amounts of
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trimethylamine (TEA) as a base catalyst. Based on their study,
the reason for the dependence seen in Figures 4 and 5 can be
attributed to the fact that base amounts strongly affect reaction
rates of both glucose isomerization and degradation of acyclic
forms of glucose and fructose.
Figure 5. Fructose selectivity (at 40–50% glucose conversion) plotted against
base amounts used in the reaction. In the case of the reactions using BaTiO
and Sr Ti , the reaction time or catalyst amount was modified: 2 h for
BaTiO ; 0.025 g of catalyst for Sr Ti . The figure does not report data using
Ti 13, because K Ti 13 (0.2 g) did not afford 40–50% glucose conversion
3
3
2 7
O
3
3
2 7
O
K
2
6
O
2
6
O
at 110 °C for 6 h. The other data are from Table 1, entries 1, 3, and 4.
Table 2 shows the results of glucose isomerization using
0
.4 g of BaTiO
base amount as 0.2 g of SrTiO
BaTiO resulted in lower glucose conversion and fructose yield
and selectivity compared to 0.2 g of SrTiO (Table 1, entry 1)
and 0.025 g of Sr Ti (Table 2). The result implies that other
3
and 0.025 g of Sr
3 2 7
Ti O , which have the same
3
. The reaction using 0.4 g of
3
3
3
2 7
O
base properties could contribute to the reactivity. Therefore, we
investigated base strength of the titanates by FT-IR
[
30-31]
spectroscopy using CHCl
3
adsorption.
Figure 6 shows the
on the
IR bands due to C-H stretching mode of adsorbed CHCl
3
Figure 3. (a) NMR spectrum of glucose-D2 reacted with SrTiO
with spectra of (b) glucose-D2 reacted in 2.5 mM NaOH aq., (c) glucose-D2,
and (d) unlabeled glucose as references.
3
in H
2
O, along
various titanates. The wavenumber of the band of C-H stretching
varied with the titanates, indicating that the titanates have
different base strength. Since the band shift to lower
wavenumber indicates stronger base, the base strength of the
titanates is in the order BaTiO
CaTiO < Sr Ti . Accordingly, BaTiO
among the titanates used in this study. The weak basicity of
3
< SrTiO
3
2 6 2 6 13
< K Ti O13 < Na Ti O
<
3
3
2
O
7
3
is the weakest base
BaTiO
BaTiO
and Sr
3
is a possible reason for the low catalytic activity of
. Conversely, a stronger base than BaTiO (e.g., SrTiO
Ti ) is considered to be effective for the isomerization
3
3
3
3
2 7
O
reaction. Therefore, we propose that base strength of solid base
catalysts also contribute to glucose isomerization performance in
Table 2. Results of glucose isomerization using BaTiO
same amount of 0.2 g of SrTiO (Table 1, entry 1).
3
and Sr
3
Ti
2
O
7
with the
Base
3
[
a]
Catalyst
Results of glucose isomerization (%)
[
b]
amount
Glucose
cov.
Fructose
yield
Mannose
yield
Fructose
(mmol)
selc.
BaTiO
.4 g
Ti
.025 g
3
3
5
0.15
0
5
3
78
0.03
0.03
0
Figure 4. Glucose conversion (red circle) and the fructose yields (black
square) on the titanates (Table 1, entries 1–6) plotted against base amounts
used for reaction (catalyst amount: 0.2 g).
Sr
3
2
O
7
33
70
0
[
a] Table Footnote. [b] …
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addition to base amount.
were used as catalysts for comparison. The catalysts were pre-treated at
−
1
2
500 °C under 100 mL min of O flow for 30 min just before use for the
glucose isomerization reaction. The solutions from the reaction were
analyzed by means of high performance liquid chromatography (HPLC)
using a JASCO LC-2000 Plus series HPLC equipped with a Shim-pack
SPR-Ca (250
mechanism on SrTiO
was used as a reactant. The reaction of glucose-D2 was performed using
mL of 1 wt% glucose-D2 aqueous solution with 0.2 g of SrTiO at 90 °C
for 1h. After reaction, H O solvent was evaporated, and the residue was
dissolved in D O to acquire a NMR spectrum.
×
7.8 mm) column. For investigating the reaction
3
, deuterated glucose at C-2 position (glucose-D2)
2
3
2
2
Characterization. X-ray diffraction (XRD) patterns were recorded on a
Rigaku MiniFlex II/AP diffractometer with Cu K radiation. The specific
surface area of the samples was determined from N adsorption using
2
Brunauer–Emmett–Teller (BET) method (BELSORP-28, BEL Japan).
The leaching of alkaline and alkaline earth metals in reaction solutions
were analyzed using a sequential inductively coupled plasma (ICP)
1
spectrometer (Thermo Jarrel Ash IRIS/AP). H-NMR spectra were
2
measured in D O on a Bruker 500 MHz NMR spectrometer. Base
amounts of the titanates were evaluated using an acid-base titration
method using phenolphthalein as an indicator. Prior to a titration, the
3
Figure 6. FT-IR spectra of CHCl adsorbed on the titanates.
titanates (0.025–0.1 g) were pre-treated in a test tube at 500 °C under O
2
flow for 30 min. After cooling to room temperature, 2 mL of water/ethanol
mixture (1/4 v/v), and then a few drops of 50 mM phenolphthalein
solution in ethanol were added to the tube. 50 mM benzoic acid solution
in ethanol was dropped into the suspension with stirring until the color of
phenolphthalein faded. The base amounts of the titanates were
evaluated from the amount of benzoic acid solution added. FT-IR spectra
Conclusions
The various titanates, including SrTiO
Na Ti Ti and Sr Ti
isomerization. In particular, SrTiO
3
,
BaTiO
catalyzed glucose
, CaTiO , and Na Ti
3 3
, CaTiO ,
2
6
O
13
,
K
2
6
O
13
,
3
2 7
O ,
3
3
2
6
O
13
3
of adsorbed CHCl were recorded on a JASCO FT/IR-6100 (JASCO Co.)
−
1
equipped with a MCT detector with a resolution of 4 cm . Samples were
pressed into wafers of 20 mm diameter. The wafers were pre-treated
offered a high fructose yield and selectivity under the reaction
conditions employed in this study (10 wt% glucose aq., 0.2 g of
catalyst, 110 °C, 1 h). The H NMR analysis of glucose-D2 after
reaction on SrTiO
are effective for the isomerization. The analysis of base
properties of the titanates using an acid-base titration method
−
1
1
under 10% O
2
flow (Ar balance, 100 mL min ) at 500 °C for 10 min. After
cooling to 150 °C, background spectra were acquired. The wafers were
3
suggested that the base sites on the titanates
−1
3
then exposed to CHCl vapor (2 L in liquid) under Ar flow (90 mL min )
3
for 10 min, and IR spectra of adsorbed CHCl were recorded.
3
and CHCl adsorption FT-IR spectroscopy indicated that the
various titanates have different base amounts and strength.
Based on the dependence of the glucose isomerization on the
base properties, we propose that both base amount and
strength of solid base catalysts (e.g., the titanates) contribute to
the efficiency of the glucose isomerization process. The results
would be useful towards developing solid base catalysts for
glucose isomerization.
Acknowledgements
This work was supported by Grant-in-Aids from the Ministry of
Education, Culture, Sports, Science and Technology (MEXT),
Japan–“Elements Strategy Initiative to Form Core Research
Center” program (since 2012) and Young Scientists (B) (No.
25820393).
Keywords: glucose isomerization • titanate • base catalyst
Experimental Section
[
[
1]
2]
M. Moliner, Y. Román-Leshkov, M. E. Davis, Proc. Natl. Acad. Sci. U. S.
A. 2010, 107, 6164.
Catalyst preparation. Alkaline and alkaline earth titanates, SrTiO
BaTiO , CaTiO , Na Ti Ti 13, and Sr Ti were prepared by a
solid state reaction. The respective alkaline carbonates (Kishida
Chemical Co., Ltd.) and TiO (JRC-TIO-8 procured from Catalysis
Society of Japan, anatase phase) as precursors were homogeneously
mixed using a ball mill in the composition ratio of each titanate, and
calcined at 1000 °C under air for 10 h. The resulting powders were
washed with hot water, and dried at 80 °C.
3
,
3
3
2
6
O13, K
2
6
O
3
2 7
O
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Hara, J. Am. Chem. Soc. 2011, 133, 4224.
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[
[
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Evaluation of catalytic activity. Glucose isomerization was performed
at 110 °C using 2 mL of 10 wt% aqueous glucose solution containing 0.2
g of catalyst unless otherwise stated. In addition to the titanate catalysts,
Y. Román-Leshkov, M. Moliner, J. A. Labinger, M. E. Davis, Angew.
Chem. Int. Ed. 2010, 49, 8954.
[
8]
J. M. Carraher, C. N. Fleitman, J.-P. Tessonnier, ACS Catal. 2015, 5,
TiO
2 3 2 3
(JRC-TIO-8), SrCO (Kishida Chemical Co., Ltd.), La O (Kishida
3162.
Chemical Co., Ltd.), hydrotalcite (Kyowa Chemical Industry Co. Ltd.)
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FULL PAPER
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ChemCatChem
10.1002/cctc.201700068
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Glucose isomerization was carried out
using various titanate catalysts,
Junya Ohyama,* Yutong Zhang, Jun Ito,
Atsushi Satsuma*
including SrTiO
Na Ti Ti
3
, BaTiO
3
, CaTiO
3
,
2
6
O
13, K
2
6
O13, and Sr
3
Ti
2
O
7
Page No. – Page No.
prepared using a conventional solid
phase method. Among the titanates,
SrTiO , CaTiO , and Na Ti O13 offered
3 3 2 6
Glucose Isomerization Using Alkaline
and Alkaline Earth Titanates
relatively high fructose yield (32%)
with high selectivity (68–78%).
Glucose isomerization on the titanates
was dependent on both base amount
and strength.
This article is protected by copyright. All rights reserved.