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ARTICLE
Journal Name
to glucaric acid or gluconic acid. The performance of photocatalytic Material and instruments
DOI: 10.1039/C9GC01647C
oxidation of glucose into organic acids seems to be not ideal,
Chemicals and solvents used in the present study were all supplied
by Aladdin Chemicals Co., Ltd. and Sinopharm Chemical Reagent
Co., Ltd., and all of them were used directly without any further
especially using pure water as the solvent. As is well known, water
is an economic and environmentally viable solvent. Therefore, it is
necessary for developing a more efficient photocatalyst to realize
the selective photocatalytic oxidation of glucose in the presence of
only water as the solvent to value-added organic acids, especially
for glucaric acid.
Considering that metal oxide semiconductors are non-toxic,
cheap and versatile materials with attractive application in
photocatalytic process, by which the selective photocatalytic
conversion of glucose to value-added chemicals would be
interesting and promising. Therefore, our initial experiments of
glucose oxidation in pure water are carried out with commercial
semiconductor photocatalysts under simulated sunlight irradiation,
purification.
1H NMR spectra measurements were conducted on a Bruker
Avance III 400 spectrometer. High-resolution mass spectra were
recorded on a Voyager DE STR MALDI-TOF mass spectrometer. The
ultraviolet-visible (UV-vis) spectra of catalyst in solution were
obtained on a Shimazu UV-2600 UV-vis spectrophotometer, and the
UV-vis diffuse reflectance spectra (DRS) of the catalyst were
examined by a Shimazu UV-2600 UV-vis spectrophotometer
4
equipped with an integrating sphere attachment using BaSO as a
reference. X-ray diffraction (XRD) patterns of the samples were
collected using a D8-advance X-ray diffractometer (German Bruker).
A study of transmission electron microscopy (TEM) was conducted
on a Tecnai G20 TEM. X-ray photoelectron spectroscopy (XPS) data
was acquired using a VG Multilab 2000 spectrometer (Thermo
Electron Corporation) and AlKα radiation was used as the X-ray
source. The electron spin resonance (ESR) spectra of the samples
were recorded on a JES-FA200 spectrometer. Surface photocurrent
such as TiO
2 3 4 2 2
(P25), ZnO, g-C N , CeO and SnO . Among them,
organic acids with a high selectivity could be obtained in the SnO
2
photocatalytic system, especially glucaric acid was only obtained
from this photocatalytic system, though this photocatalytic system
showed a low conversion of glucose. However, this behavior
derived from SnO
selective photocatalytic oxidation of glucose to value-added organic
acids could be achieved by using SnO -based photocatalyst. It is well
known that the surface characteristics of photocatalyst are very
2
raised the interesting possibility that highly
(SPC) measurements were obtained from
a Corrtest CS350
2
electrochemical workstation.
2
3,
24
important
for
the
catalytic
performance.
Metallothioporphyrazines (MPzs) bearing sulfur-containing groups Synthesis of iron tetra(2,3-bis(butylthio)maleonitrile)porphyrazine
in the periphery of the porphyrin macrocycle have an extensive
The molecular structure of FePz(SBu)
the metal-free tetra(2,3-bis(butylthio)maleonitrile)porphyrazine
Pz(SBu) ) was synthesized by the following procedure. 2,3-
bis(butylthio)maleonitrile (0.50 g) were added into the magnesium
butoxide (100 mL), then the mixture was stirred under reflux for 48
h in a nitrogen atmosphere. After that, the crude product was
obtained by filtration, and then washed with methanol
until the filtrate was colourless. In order to remove the central
metal, the obtained product was added into the trifluoroacetic acid
8
was shown in Fig. S1. Firstly,
system of delocalized π electrons and a strong absorption in visible
light region, which have great potential in utilization of sunlight.25-27
Moreover, some studies suggested that semiconductor
(H
2
8
photocatalysts, such as g-C
effectively improve their photocatalytic activity.
when g-C coupled with CoPz, the strong interaction of CoPz with
g-C
3 4
N and ZnO, coupled with MPz can
2
8, 29
For example,
3 4
N
3
N
4
can disable the hydroxyl radical (·OH) generation by g-C
3
N
4
1
and promote the singlet oxygen ( O
2
) generation on the CoPz sites
under simulated sunlight irradiation, resulting in the excellent
photocatalytic activity for selective oxidation of 5-
(50 mL) and stirred for 12 h in the dark. After removing the
trifluoroacetic acid, the dark purple products were obtained, which
were further purified by a column chromatography with silica gel,
the eluent was dichloromethane/petroleum ether (3:1, v/v). The
2
8
hydroxymethyfurfural to 2,5-furandicarboxylic acid. Therefore,
combining SnO and MPz to prepare a composite photocatalyst
2
with higher photocatalytic activity seems to be extraordinarily vital
to promote glucose transformation more efficiently.
1
target product was characterized with UV-vis spectrum, H NMR
spectrum and MALDI-TOF MS. The characteristic structure datas for
the target product are as follows: The yield was 60% (1.2 g); UV-vis
In this work, iron thioporphyrazine modified SnO
SnO /FePz(SBu) ) composite was prepared by immobilizing iron
tetra(2,3-bis(butylthio)maleonitrile)porphyrazine (FePz(SBu) ) onto
the SnO surface. Using SnO /FePz(SBu) as photocatalyst, selective
2
(
2
8
spectrum λmax (in dichloromethane): Q-band: 640 nm and 711 nm;
8
1
Soret-band: 505 nm; B-band: 354 nm; H NMR spectrum (in CDCl
3
):
2
2
8
4
1
.10-4.14 (t, 16H), 1.89 (m, 16H), 1.67 (m, 16H), 0.90-0.97 (t, 24H), -
.12 (s, 2H); MALDI-TOF MS: m/z = 1019.5 [M+H] . See also Figs. S2-
photocatalytic oxidation of glucose in water was carried out in
aerated conditions under simulated sunlight irradiation. The effects
of catalyst loading amount, glucose concentration and other related
reaction parameters on the photocatalytic oxidation of glucose
+
S4.
Subsequently, metal-free H
87 mg) were added into N,N-dimethyl formamide (DMF) (50 mL).
2 8
Pz(SBu) (0.10 g) and iron(II) acetate
(
were studied. It turned out that SnO
2
/FePz(SBu)
8
was an efficient
o
Afterwards, the mixture was stirred at 70 C for 10 h in a nitrogen
atmosphere. When the reaction was completed, the crude product
was obtained by removing the solvent, which was then added into
dichloromethane (20 mL). The precipitate was collected by filtration
and further purified by a column chromatography with silica gel, the
eluent was hexane/dichloromethane (3:1, v/v). The characteristic
structure datas for the target product are as follows: The yield was
photocatalyst for oxidation of glucose to organic acids, such as
glucaric acid, gluconic acid and formic acid. In addition, the
synergistic effect between FePz(SBu) and SnO and the possible
8 2
pathway of photocatalytic oxidation of glucose were also discussed.
Experimental
2
| J. Name., 2012, 00, 1-3
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