Visible-light-driven selective oxidation of glucose in water with H-ZSM-5 zeolite supported biomimetic photocatalyst

Article abstract of DOI:10.1016/j.jcat.2019.04.044

A new iron tetra(2,3-bis(butylthio)maleonitrile)porphyrazine (FePz(SBu)₈)has been synthesized, then it was loaded on H-ZSM-5 zeolite to obtain a supported biomimetic photocatalyst H-ZSM-5/FePz(SBu)₈. Using H₂O₂ as oxidant, the photocatalytic selective oxidation of glucose in water under visible light (λ ≥ 420 nm)irradiation was carried out in presence of H-ZSM-5/FePz(SBu)₈. Under such conditions, the glucose can be efficiently converted into value-added chemicals such as glucaric acid, gluconic acid, arabinose, glycerol and formic acid. More importantly, in comparison with pure FePz(SBu)₈ and pure H-ZSM-5 zeolite, the H-ZSM-5/FePz(SBu)₈ exhibited a higher photocatalytic activity for glucose oxidation and the formation of glucaric acid was observed only when H-ZSM-5/FePz(SBu)₈ was used, deriving from the synergistic effect between FePz(SBu)₈ and H-ZSM-5 zeolite. Some reaction parameters of glucose oxidation catalyzed by the H-ZSM-5/FePz(SBu)₈ were discussed, such as loading amount of FePz(SBu)₈, H₂O₂:glucose ratio, glucose concentration, and so on. It was demonstrated that the Soret-band of FePz(SBu)₈ contributed more to the visible light photocatalytic activity than the Q-band during the photocatalytic process. The stability of H-ZSM-5/FePz(SBu)₈ during the photocatalytic process was further evaluated by the reusability test. In addition, the generation of reactive oxygen species was determined by electron spin resonance (ESR)technology and scavenger experiments. A possible reaction pathway of glucose oxidation was also discussed.

Full text of DOI:10.1016/j.jcat.2019.04.044

Journal of Catalysis 374 (2019) 297–305
Contents lists available at ScienceDirect
Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat
Visible-light-driven selective oxidation of glucose in water
with H-ZSM-5 zeolite supported biomimetic photocatalyst
⇑
Rui Chen, Changjun Yang , Quanquan Zhang, Bingguang Zhang, Kejian Deng
Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, Hubei Province, College of Chemistry and Material Science,
South-Central University For Nationalities, Wuhan 430074, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A new iron tetra(2,3-bis(butylthio)maleonitrile)porphyrazine (FePz(SBu) ) has been synthesized, then it
8
Received 20 February 2019
Revised 27 April 2019
Accepted 30 April 2019
was loaded on H-ZSM-5 zeolite to obtain a supported biomimetic photocatalyst H-ZSM-5/FePz(SBu)
Using H as oxidant, the photocatalytic selective oxidation of glucose in water under visible light
k ꢀ 420 nm) irradiation was carried out in presence of H-ZSM-5/FePz(SBu) . Under such conditions,
the glucose can be efficiently converted into value-added chemicals such as glucaric acid, gluconic acid,
arabinose, glycerol and formic acid. More importantly, in comparison with pure FePz(SBu) and pure H-
ZSM-5 zeolite, the H-ZSM-5/FePz(SBu) exhibited a higher photocatalytic activity for glucose oxidation
and the formation of glucaric acid was observed only when H-ZSM-5/FePz(SBu) was used, deriving from
the synergistic effect between FePz(SBu) and H-ZSM-5 zeolite. Some reaction parameters of glucose oxi-
dation catalyzed by the H-ZSM-5/FePz(SBu) were discussed, such as loading amount of FePz(SBu)
:glucose ratio, glucose concentration, and so on. It was demonstrated that the Soret-band of FePz
SBu) contributed more to the visible light photocatalytic activity than the Q-band during the photocat-
alytic process. The stability of H-ZSM-5/FePz(SBu) during the photocatalytic process was further evalu-
8
.
2 2
O
(
8
8
Keywords:
Glucose
Selective oxidation
H-ZSM-5 zeolite
Iron thioporphyrazine
Photocatalysis
8
8
8
8
8
,
2 2
H O
(
8
8
ated by the reusability test. In addition, the generation of reactive oxygen species was determined by
electron spin resonance (ESR) technology and scavenger experiments. A possible reaction pathway of glu-
cose oxidation was also discussed.
Ó 2019 Elsevier Inc. All rights reserved.
1
. Introduction
With the increasing focus on the depletion of petroleum-based
photocatalysis in the upgrading of glucose is getting increasing
attention. Compared to those energy intensive processes, photo-
catalytic transformation can be efficiently driven by sunlight and
performed at ambient temperature and pressure, such a light dri-
ven process seems to be an environmentally friendly, valuable
and efficient method for glucose oxidation. Recent advances sug-
gest that partly selective photocatalytic oxidation of glucose to
value-added chemicals can be carried out in aqueous media or a
resources and environmental pollution, the use of biomass for pro-
ducing value-added chemicals or other fuels has attracted wide
attention because of its characters of renewable, abundance,
cheapness and less pollution. Glucose is the most diffuse and
cheapest monosaccharide for it can be gained first hand from the
hydrolysis of cellulose, the most abundant renewable biomass on
Earth [1,2]. The oxidation of glucose can afford a wide variety of
value-added chemicals used in the fields of food additive, pharma-
ceutical and fine chemicals [3,4]. Particularly, glucaric acid pro-
duced from the oxidation of both terminal groups is an emerging
platform chemical using as a building block chemical. It has been
considered as a top value-added chemical from biomass [5]. The
traditional oxidation of glucose to value-added chemicals has been
extensively investigated using enzymes and heterogeneous
catalysts based on metal nanoparticles [6–8]. The application of
2
mixed solvent of water and acetonitrile using TiO -based catalysts
under ultraviolet (UV) light, obtaining a variety of oxidation prod-
ucts including carboxylic acids (glucaric acid, gluconic acid, lactic
acid and formic acid) and other oxygenated hydrocarbons (arabi-
nose, erythrose, arabitol, xylitol and glyceraldehyde) [9–14]. It’s
2 2
also worth noting that TiO and Ag/TiO catalysts can also convert
glucose to value-added chemicals under visible light because of the
formation of a ligand to metal charge transfer complex and the
plasmonic effect of Ag, respectively [15,16]. In the light of available
energy, UV light only accounts for less than 5% of the total solar
energy, while visible light makes up the majority of solar energy
[
17]. Considering the efficient use of solar energy, it is fundamental
⇑
Corresponding author.
E-mail address: yangchangjun@mail.scuec.edu.cn (C. Yang).
that we devise new visible-light-driven photocatalyst that better
https://doi.org/10.1016/j.jcat.2019.04.044
021-9517/Ó 2019 Elsevier Inc. All rights reserved.
0

2
98
R. Chen et al. / Journal of Catalysis 374 (2019) 297–305
utilize solar energy and still exhibit high activity and selectivity for
organic synthetic reaction.
Metallothioporphyrzines (MPzs) possessing sulfur-containing
groups in macrocyclic periphery are a type of macrocyclic com-
High-resolution mass spectra were obtained on an AB/5800
MALDI-TOF mass spectrometer. The ultraviolet-visible (UV–vis)
spectra of catalyst in solution were measured by a Shimazu
UV-2600 UV–vis spectrophotometer, and the UV–vis diffuse
reflectance spectra (DRS) of supported catalysts were also
acquired by the Shimazu UV-2600 UV–vis spectrophotometer
pound which have an extensive system of delocalized
p electrons.
They have attracted an increasing interest in recent years due to
their peculiar photophysical, photochemical and electrochemical
properties [18–20]. Specifically, MPzs are considered as biomi-
metic photocatalysts because of their strong absorption in the vis-
ible region, which can nicely meet the purpose of using sunlight. In
our previous research, it has been reported that MPzs exhibited a
unique photocatalytic activity for activating hydrogen peroxide
or dioxygen under visible light, which are applied to the selective
organic transformations under mild conditions. For example, using
cobalt thioporphyrazine as photocatalyst, the benzyl alcohol and
amine could be highly selectively oxidized to benzoic acid and
imine under visible light irradiation, respectively [21,22]. The easy
excitation by visible light and the ability of participating in various
photophysico-chemical processes make MPzs as promising candi-
dates for excellent photocatalysts.
equipped with an integrating sphere attachment, using BaSO
4
1
as the reference material. H NMR spectra were recorded with
a Bruker Avance III 400 spectrometer. The morphology of the
catalyst was characterized by scanning electron microscope
(SEM) (SU8010, HITACHI) and transmission electron microscopy
(TEM) (Tecnai G20, USA). The X-ray photoelectron spectra
(XPS) analysis of the catalysts was recorded on a VG Multilab-
2000 spectrometer (Thermo Electron Corporation) with
monochromatic Mg K source and a charge neutralizer. The
X-ray diffraction (XRD) patterns were conducted using
a
a
a
D8-advance powder diffractometer (German Bruker). The reac-
tive oxygen species were determined by electron spin resonance
(ESR) spectra, which were performed by a JES-FA200 spectrome-
ter. The photocurrents were measured with a CHI 760E electro-
chemical workstation.
The molecular structure of MPz can be modified by modulating
the peripheral substitutes, changing the central metal or expand-
ing the
s(butylthio)maleonitrile)porphyrazine (FePz(SBu)
sized, the molecular structure of FePz(SBu) was shown in Fig. 1.
Then the FePz(SBu) complex was loaded onto the H-ZSM-5 zeolite
which has large specific surface area and high chemical stability,
obtaining the photocatalyst H-ZSM-5/FePz(SBu) . Using H as
oxidant, the photocatalytic oxidation of glucose under visible light
p
-electron system [23,24]. Herein, a new iron tetra(2,3-bi
2
.2. Synthesis of iron tetra(2,3-bis(butylthio)maleonitrile)porphyrazine
8
) was synthe-
8
The metal-free tetra(2,3-bis(butylthio)maleonitrile)porphyra
8
2 8
zine (H Pz(SBu) ) was synthesized in the following procedure.
Magnesium butoxide solution was firstly prepared by the reaction
of magnesium tablet (0.06 g) with butanol (100 mL) at reflux
temperature for 48 h. Then the precursor 2,3-bis(butylthio)
maleonitrile (3 g) was added into the preceding magnesium butox-
ide solution, a dark-green solution was obtained after reaction for
8
2 2
O
(
(
k ꢀ 420 nm) irradiation was carried out by using H-ZSM-5/FePz
SBu) photocatalysts in water. It turned out that FePz(SBu) was
8
8
an efficient biomimetic photocatalyst for oxidation of glucose to
value-added chemicals, such as glucaric acid, gluconic acid, arabi-
nose, glycerol and formic acid. Moreover, the active oxygen species
generated in the photocatalytic process were identified and the
possible reaction pathway of glucose oxidation was also discussed.
2
4 h at reflux temperature under stirring condition. Removal of the
solvent by reduced pressure distillation gave a crude solid formed.
The obtained products were subsequently dissolved in trifluo-
roacetic acid (5 mL), and the mixture was stirred for additional
8
h in dark in order to remove the center metal magnesium. After
that, the solution was plunged into purified water to deposit the
target product metal-free H Pz(SBu) , the dark purple products
2
. Experimental
2
8
were obtained by filtration, which were thoroughly washed with
ammonia solution, water and methanol. The target products
formed was further purified on silica gel chromatography column
2
.1. Materials and instruments
All chemicals and solvents used in this work were purchased
using dichloromethane (CH
2
Cl
2
)/petroleum ether (PE) (1:1, v/v)
Pz(SBu) was characterized with
NMR spectrum, the characteristic
structure datas for the product were shown as following: 2.18 g
yield 69%); UV–vis kmax (in CH Cl ): Q-band: 712 nm and
40 nm; Soret-band: 507 nm, B-band: 350 nm, see Fig. 2(A);
from Aladdin Chemicals Co., Ltd and Sinopharm Chemical Reagent
Co., Ltd, and all of them were used as received without further
purification.
as an eluent. The target product H
2
8
1
UV–vis spectrum and
H
(
6
2
2
1
H
NMR (400 MHz, CDCl
3
): d = 4.1 (t, 2H, -SCH
2
-), 1.9 (m, 2H,–CH
2
–),
1
.6 (m, 2H, –CH
Fig. 2(B).
Metal-free
0.312 g) were respectively added into pyridine (50 mL), then the
2
–), 0.9 (t, 3H, –CH
3
), ꢁ1.1 (t, 2H, –NH-), see
2 8
H Pz(SBu)
(0.308 g) and iron acetylacetonate
(
mixture was continuously stirred for 10 h at 115 °C, the color of
the solution changed from purple to green during the reaction.
After the reaction was completed, the target product FePz(SBu)
8
was obtained by removing the solvent pyridine using reduced
pressure distillation, which was further purified on silica gel chro-
matography column using CH
The target product FePz(SBu)
2
Cl
2
/methanol (9:1, v/v) as an eluent.
was characterized with UV–vis
8
spectrum and MALDI-TOF MS, the characteristic structure datas
for the product were shown as following: 0.234 g (yield 72%);
UV–vis kmax (in CH Cl ): Q-band: 644 nm; Soret-band: 501 nm,
2 2
B-band: 366 nm, see Fig. 3(A); MALDI-TOF MS: m/z = 1073.3
[M+H] , see Fig. 3(B).
Fig. 1. Molecular structure of iron tetra(2,3-bis(butylthio)maleonitrile)por-
+
phyrazine (FePz(SBu)
8
).

R. Chen et al. / Journal of Catalysis 374 (2019) 297–305
299
2 8 2 2
Pz(SBu) in CH Cl
(A) and the 1H NMR
Fig. 2. UV–vis spectrum of metal-free H
spectrum of H Pz(SBu) in CDCl (B).
Fig. 3. UV–vis spectrum of FePz(SBu)
SBu) (B).
8
in CH
2
Cl
2
(A) and the MALDI-TOF MS of FePz
2
8
3
(
8
2
.3. Preparation of H-ZSM-5/FePz(SBu)
8
2 2
H O :glucose ratio of 3.3:1 was added into the above suspension
and continually stirred for 10 min. After that, the reaction mixture
was irradiated by a Xe lamp (Bejing China Education Au-light Co.,
Ltd) with a 420 nm cutoff filter. In order to control the photocat-
alytic reaction at ambient temperature, the cooling water was cir-
culated through the circling water-cooled jacket located around
the reactor. Sample solutions were taken at specific times and then
ZSM-5 zeolite was synthesized in the light of the reported liter-
ature [25]. To obtain H-type ZSM-5 (H-ZSM-5) zeolite, the pre-
ꢁ1
pared ZSM-5 zeolite was added into 1 L 1 mol L
4 3
NH NO
aqueous solution, which was further stirred at room temperature
for 24 h. The target product H-ZSM-5 zeolite was obtained by fil-
tration and washed thoroughly with ethanol and water, which
was then dried at 120 °C for 12 h and finally calcined at 550 °C
for 4 h, obtaining H-ZSM-5 zeolite.
immediately filtered by 0.22 lm membranes before analyses.
The glucose conversion and the selectivity of oxidation product
were monitored using a Dionex UltiMate 3000 HPLC system
equipped with a refractive index (RI) (ERC RefractoMax520) detec-
tor, a Shodex SUGAR SH-1011 column (8 mm ꢂ 300 mm) and an
In a typical preparation procedure on H-ZSM-5/FePz(SBu)
8
,
3
0 mg FePz(SBu) was firstly dissolved in 30 mL CH Cl by means
8
2
2
ꢁ1
of ultrasonication. Then 1 g H-ZSM-5 zeolite was added into the
above solution under the action of magnetic stirring, the mixture
was stirred continuously for 5 h. After that, the supported photo-
2 4
aqueous 0.4 mmol L H SO solution as an eluent with a flow rate
ꢁ1
of 0.6 mL min were used. The products generated during the
reaction were identified by comparison with standard samples
catalyst H-ZSM-5/FePz(SBu)
vent CH Cl using reduced pressure distillation, the content of
FePz(SBu) supported on the H-ZSM-5 zeolite was equal to 3%. A
range of H-ZSM-5/FePz(SBu) photocatalysts with different content
of FePz(SBu) , such as 1%, 5% and 7%, were also prepared on the
grounds of the same experimental process.
8
was obtained by removing the sol-
and
further
confirmed
by
high
performance
liquid
2
2
chromatography-mass (HPLC-MS). HPLC-MS analysis was per-
formed on a Shimadzu LCMS-8050 triple quadrupole mass spec-
trometer with C18 column (4.6 mm ꢂ 250 mm).
8
8
8
The conversion of glucose and selectivity of oxidation products
were calculated using the following formulas.
½
glucoseꢃ ꢁ ½glucoseꢃ
i
t
Conversion ¼
Selectivity ¼
ꢂ 100%
ꢂ 100%
2
.4. Photocatalytic oxidation of glucose
½glucoseꢃ
i
½
productꢃ
i
t
In a typical photocatalytic reaction, 30 mg H-ZSM-5/FePz(SBu)
8
½
glucoseꢃ ꢁ ½glucoseꢃ
t
ꢁ
1
photocatalysts were firstly dispersed into 30 mL 3 mmol L aque-
ous glucose solution in a Pyrex vessel with a circling water-cooled
jacket by ultrasonication for 5 min. Then an additional H
In the above formulas, [glucose]
tration of substrate glucose. [glucose]
i
stands for the initial molar concen-
and [product] represent the
2
O
2
with a
t
t

3
00
R. Chen et al. / Journal of Catalysis 374 (2019) 297–305
molar concentration of substrate glucose and a product after t time
of reaction, respectively.
Figs. S2 and 5(A), respectively. From Figs. S2 and 5(A), it is dis-
played that the prepared H-ZSM-5 zeolite nanoparticles are spher-
8
ical in shape. After a small quantity of FePz(SBu) complex were
supported on the H-ZSM-5 zeolite, such as 1%, 3%, 5% and 7%, the
peak positions of H-ZSM-5 zeolite did not change in the XRD pat-
3
. Results and discussion
terns of H-ZSM-5/FePz(SBu)
8
, indicating that the loading process
3
.1. Characterization of metal-free thioporphyrazine and iron
of FePz(SBu)
zeolite.
8
has little effect on the bulk structure of H-ZSM-5
thioporphyrazine
8
The SEM image of H-ZSM-5/FePz(SBu) (5%) was shown in Fig. 5
B). Compared with the morphology of bare H-ZSM-5 zeolite (Fig. 5
A)), it could be seen that the shape of the H-ZSM-5 zeolite
2 8
The UV–vis absorption spectrum of metal-free H Pz(SBu) in
CH Cl was shown in Fig. 2(A). It could be seen that three types
2 2
of characteristic bands, such as Q-band at 712 nm and 640 nm,
Soret-band at 507 nm and B-band at 350 nm, presented in the
(
(
remained essentially unchanged before and after loading with
FePz(SBu) , which is in good agreement with the above XRD anal-
8
2 8
spectra of H Pz(SBu) . Specifically, the splitting two peaks of Q-
ysis. However, a net structure of film-like layer (see yellow ring in
Fig. 5(B)) was clearly presented on the surface of H-ZSM-5 zeolite
band is an important feature of free-base porphyrazine. Moreover,
1
the H NMR spectrum of H
B). It shows four kinds of hydrogens, namely, 4.1 (t, 2H, –SCH
.9 (m, 2H,–CH –), 1.6 (m, 2H, –CH –) and 0.9 (t, 3H, –CH ) in the
2
Pz(SBu)
8
in CDCl
3
was shown in Fig. 2
for H-ZSM-5/FePz(SBu)
8
sample, which should be the deposited
is distributed on the surface
(
1
2
–),
FePz(SBu) , that is to say, FePz(SBu)
8
8
2
2
3
of H-ZSM-5 zeolite. This result indicated that the FePz(SBu)
successfully loaded on the H-ZSM-5 zeolite.
8
was
peripheral butylthio group, and the inner hydrongen ꢁ1.1 (t, 2H, –
1
NH–) of macrocycle. The result of H NMR further verifies the syn-
UV–vis DRS was carried out to analyze the optical spectral
response of pure H-ZSM-5 zeolite and H-ZSM-5/FePz(SBu) , as
thesis of metal-free H
The as-prepared metal-free H
iron acetylacetonate in pyridine solution to generate the target
product FePz(SBu) with a yield of 72%. The UV–vis absorption
spectrum of FePz(SBu) in CH Cl was presented in Fig. 3(A). It is
obvious that the splitted Q-band disappeared in the spectrum of
FePz(SBu) in comparison to that of metal-free H Pz(SBu) , indicat-
2 8
Pz(SBu) .
8
2
8
Pz(SBu) directly reacted with
shown in Fig. 6. From Fig. 6, it was observed that the support H-
ZSM-5 zeolite showed poor absorption from 300 nm to 800 nm.
8
But for H-ZSM-5/FePz(SBu)
ture peaks of FePz(SBu) molecule such as Q-band and B-band, this
provides further evidence that FePz(SBu) successfully loaded onto
8
samples, all samples display the fea-
8
2
2
8
8
8
2
8
the surface of H-ZSM-5 zeolite, which is also consistent with the
SEM observation. Meanwhile, the UV-vis DRS datas provide addi-
tional important information that H-ZSM-5/FePz(SBu) samples
8
have intensive absorption in the visible light region, implying that
they can be served as visible light photocatalysts to drive the
photocatalytic reactions.
ing that the coordination reaction of iron ion had successfully
occurred under current conditions. Meanwhile, the MALDI-TOF
+
MS of FePz(SBu)
8
has m/z = 1073.3 [M+H] as shown in Fig. 3(B),
which is in good consistent with the molecular weight of FePz
SBu) . From the XPS analysis as shown in Fig. S1, it could be
observed that the presence of the Fe(II) peaks at 720.95 eV and
08.20 eV, which correspond to the binding energies of Fe2p1/2
and Fe 2p3/2 [26].
(
8
7
3
.3. Photocatalytic performance
8
The photocatalytic performance of H-ZSM-5/FePz(SBu) photo-
3
.2. Characterization of H-ZSM-5/FePz(SBu)
8
catalyst for oxidation of glucose in water was carried out under vis-
ible light (k ꢀ 420 nm) irradiation. Table 1 shows the results of
exploratory experiments of the glucose oxidation under different
conditions, obtaining insight into the excellent performance of
Fig. 4 shows that the X-ray diffraction (XRD) patterns of pure H-
ZSM-5zeolite and H-ZSM-5/FePz(SBu) samples. As can be seen in
Fig. 4a, the prepared H-ZSM-5 zeolite sample shows Bragg diffrac-
tion peaks with 2h at 7.98°, 8.78°, 23.09°, 23.88° and 24.41°, indi-
cating that the sample consists of highly crystalline MFI phase
8
the H-ZSM-5/FePz(SBu)
value-added chemicals. In absence of any catalyst, the conversion
of glucose is only 2.2% in presence of H under visible light irra-
8
catalyst for oxidation of glucose to
2 2
O
[
25,27]. The morphology of the prepared H-ZSM-5 zeolite sample
diation and the oxidation product is arabinose (Table 1, Entry 1). As
it is seen, 4.9% glucose conversion is obtained in presence of pure
was also observed by TEM and SEM, which were shown in
FePz(SBu)
glycerol and formic acid, under such conditions, the mass of FePz
SBu) catalyst is equal to that in the H-ZSM-5/FePz(SBu) (5%)
8
, the oxidation products are gluconic acid, arabinose,
(
8
8
composite in order to compare the photocatalytic activity (Table 1,
Entry 2). The reaction of glucose oxidation could also occur in pres-
ence of H-ZSM-5 zeolite with 1.9% conversion, producing a very
small quantity of gluconic acid and arabinose (Table 1, Entry 3).
3
+
It is known that Fe /H
therefore, the glucose conversion in presence of FeCl
ducted under visible light irradiation. Although 99.1% glucose con-
version is achieved on FeCl catalyst, only formic acid with a
selectivity of 6.8% is obtained (Table 1, Entry 4). Compared with
the above several system, H-ZSM-5/FePz(SBu) displays the excel-
2
O
2
system is the famous Fenton reagent,
3
is also con-
3
8
lent performance of oxidation of glucose to value-added chemicals,
five value-added products such as glucaric acid, gluconic acid, ara-
binose, glycerol and formic acid are obtained, the total selectivity
for five products is 79.8% of 35.8% glucose conversion (Table 1,
Entry 5). The total selectivity is less than 100%, maybe because
the glucose is mineralized to CO
finding is that glucaric acid is obtained with a selectivity of
13.1% in the H-ZSM-5/FePz(SBu) photocatalytic system, while
2 2
and H O. The most interesting
Fig. 4. X-ray diffraction (XRD) patterns of pure H-ZSM-5 zeolite and H-ZSM-5/FePz
(
SBu)
SBu)
8
. (a) pure H-ZSM-5 zeolite; (b) H-ZSM-5/FePz(SBu)
8
(1%); (c) H-ZSM-5/FePz
(7%).
(
8
(3%); (d) H-ZSM-5/FePz(SBu) (5%); (e) H-ZSM-5/FePz(SBu)
8
8
8

R. Chen et al. / Journal of Catalysis 374 (2019) 297–305
301
8
Fig. 5. SEM images of pure H-ZSM-5 zeolite (A) and H-ZSM-5/FePz(SBu) (5%) (B).
ment of the conversion rate of glucose (Fig. S3), indicating that
the photocatalytic activity of the H-ZSM-5/FePz(SBu) depends
8
on the intensity of incident light. These results clearly display that
the glucose oxidation is undoubtedly driven by visible light. When
O
2
is inlet, the glucose conversion over the H-ZSM-5/FePz(SBu)
only about 1.5% (Table 1, Entry 7).
Photocatalytic oxidation of glucose in water in presence of Na-
ZSM-5/FePz(SBu) or SiO /FePz(SBu) were also performed under
8
is
8
2
8
the same reaction conditions, it was found that the photocatalytic
activities of both catalysts were lower than that of H-ZSM-5/FePz
(
(
SBu)
Table 1, entries 8 and 9), indicating that H-ZSM-5 zeolite is a bet-
for glucose oxidation in water. In addi-
8
and no glucaric acid was formed in both catalytic systems
ter support for FePz(SBu)
8
tion, the photocatalytic oxidation of glucose were conducted
under irradiation of k = 500 nm visible light and k = 650 nm visible
8
light in presence of H-ZSM-5/FePz(SBu) . It could be seen that the
Fig. 6. UV–vis diffuse reflectance spectra (DRS) of pure H-ZSM-5 zeolite and H-
ZSM-5/FePz(SBu)
glucose conversion obtained with k = 500 nm visible light is higher
than that obtained with k = 650 nm visible light (Table 1, entries 10
and 11). Therefore, it was proposed that the Soret-band of FePz
8
.
no glucaric acid is formed under the conditions of pure FePz(SBu)
or pure H-ZSM-5 zeolite. These results indicate that there exists a
synergistic effect between FePz(SBu) and H-ZSM-5 zeolite, which
is beneficial to the oxidation of glucose and the formation of glu-
caric acid. In contrast, almost no conversion of glucose occurred
8
(SBu) contributed more to the visible light photocatalytic activity
than the Q-band during the photocatalytic process.
8
8
The effect of loading amounts of FePz(SBu)8 on the photocat-
alytic oxidation of glucose to value-added chemicals was further
examined, as shown in Fig. 7. Inspection of Fig. 7 suggests that
the glucose conversion improved with increasing the loading
amounts, which changes from 6.4% to 46% in the loading range
in the dark over the H-ZSM-5/FePz(SBu)
8
catalyst (Table 1, Entry
6
). Meanwhile, increasing the light intensity results in enhance-
Table 1
The photocatalytic oxidation of aqueous glucose under different conditions.
a
Entry
Catalyst
Conversion/%
Selectivity/%
P Selectivity/%
GAA
GOA
Ab
Gly
FA
1
2
without
FePz(SBu)
H-ZSM-5
2.2
4.9
1.9
99.1
35.8
–
1.5
21.7
6.0
–
–
–
–
13.1
–
–
–
–
–
87.1
31.8
54.3
–
17.3
–
80.5
12.8
25.3
22.2
12.4
–
10.6
–
–
1.7
–
–
7.8
–
6.8
13.0
–
87.1
77.8
90.0
6.8
79.8
–
97.9
65.7
61.7
85.4
90.1
b
8
27.5
35.7
–
31.9
–
17.4
34.1
21.8
24.6
33.1
3
4
5
FeCl
3
H-ZSM-5/FePz(SBu)
H-ZSM-5/FePz(SBu)
H-ZSM-5/FePz(SBu)
8
8
8
(5%)
(5%)
(5%)
c
6
d
7
–
–
8
9
Na-ZSM-5/FePz(SBu)
SiO /FePz(SBu) (5%)
8
(5%)
8.4
8.4
7.3
6.8
10.3
6.2
20.2
16.0
2
8
e
1
1
0
1
H-ZSM-5/FePz(SBu)
H-ZSM-5/FePz(SBu)
8
(5%)
(5%)
14.3
7.9
11.1
21.9
f
8
a
ꢁ1
Reaction conditions: catalyst (30 mg), aqueous glucose (3 mmol L , 30 mL), H
2
O
2
with a H
2
O
2
:glucose ratio of 3.3:1, k ꢀ 420 nm visible light (light intensity:
ꢁ
2
1
.70 W cm ), reaction for 4 h.
b
FePz(SBu)
8
(1.5 mg).
Without visible light irradiation.
Without adding H
c
d
e
f
2 2
O .
ꢁ2
k = 500 nm visible light (light intensity: 1.70 W cm ).
ꢁ2
k = 650 nm visible light (light intensity: 1.70 W cm ). (Note: GAA-glucaric acid, GOA-gluconic acid, Ab-arabinose, Gly-glycerol, FA-formic acid.).

3
02
R. Chen et al. / Journal of Catalysis 374 (2019) 297–305
could be reached up to 92.4%, while the total selectivity for glucaric
acid and gluconic acid is up to 45.9%. Meanwhile, a different evolu-
tion trend for selectivity of each product is also observed. For
example, a maximum selectivity of glucaric acid is acquired when
2
H O
2
:glucose ratio is 3.3:1, and then a gradual reduction of the
selectivity is detected when H :glucose ratio increases from
.3:1 to 4.4:1. The selectivity in gluconic acid shows the highest
value of 37.5% in a low H :glucose ratio, such as 2.2:1, a further
increase in H :glucose ratio gradually decreases the selectivity
2 2
O
3
2 2
O
2 2
O
of gluconic acid, a similar trend to three other compounds is also
observed.
Subsequently, the effect of glucose concentration on the photo-
catalytic oxidation of glucose to value-added chemicals was fur-
ꢁ1
ꢁ1
ther investigated in the range from 1 mmol L to 10 mmol L
,
ꢁ1
as showed in Fig. S4. At a low concentration of 1 mmol L , the con-
version of glucose could reach up to 88.7% after reaction for 4 h,
but the total selectivity of oxidation products is only about
13.8%, maybe because the generated products suffer from the
attack of active oxygen species to cause the deep oxidation in a
low substrate concentration. With increasing the glucose concen-
tration, the total selectivity of oxidation products exhibits a signif-
icant improvement, for the probability that active oxygen species
attack the substrate is markedly increased in a high substrate con-
centration. It is noteworthy that the total selectivity for glucaric
acid and gluconic acid reaches up to 45% when glucose concentra-
Fig. 7. Effect of loading amounts of FePz(SBu)
8
on the photocatalytic oxidation of
glucose under visible light irradiation. Reaction conditions: catalyst (30 mg),
ꢁ
1
2 2 2 2
aqueous glucose (3 mmol L , 30 mL), H O with a H O :glucose ratio of 3.3:1,
ꢁ
2
k ꢀ 420 nm visible light (light intensity: 1.70 W cm ), reaction for 4 h. a: glucaric
acid; b: gluconic acid; c: arabinose; d: glycerol; e: formic acid. (Note: black bar and
color bar represent the glucose conversion and product selectivity, respectively.)
from 1% to 7%. It indicates that the loading amount of FePz(SBu)
has a positive effect on the photocatalytic activity of H-ZSM-5/
FePz(SBu) . Different loading amounts of FePz(SBu) have a limited
8
8
8
impact on the total selectivity of oxidation products. In all cases,
the gluconic acid is the main oxidation product, which has a max-
imum selectivity with 44.7% when the loading is 1%. While by
increasing the loading amount there exists a downward trend for
the selectivity of glucaric acid. The arabinose exhibits a high selec-
ꢁ1
tion is 3 mmol L . While when the substrate concentration
ꢁ1
exceeds 3 mmol L , no remarkable change of the glucose conver-
sion is observed, it is probably because of the limited amount of
oxidant.
tivity when the loading amount of FePz(SBu)
ering the substrate conversion and product selectivity, it appears
that the best loading of FePz(SBu) for glucose oxidation under
the experimental conditions used in this study is 5%.
8
exceeds 1%. Consid-
3
.5. Reusability of the photocatalyst
8
The recyclability of catalyst plays a significant role in its indus-
trial application. For this purpose, the repeatability of H-ZSM-5/
FePz(SBu) photocatalyst in the photocatalytic conversion of glu-
cose was examined. As shown in Fig. 9, it can be seen that about
0.6% of glucose is converted at the first run, the conversion of glu-
8
3.4. Effect of reaction conditions for glucose oxidation
4
The effect of H
of glucose to value-added chemicals was examined in presence of
H-ZSM-5/FePz(SBu) (5%). As illustrated in Fig. 8, it could be seen
that the conversion of glucose increases from 19.1% to 86.3% with
a variation of H :glucose ratio from 2.2:1 to 4.4:1. However, the
total selectivity of oxidation products shows a downward trend
with the increase of H :glucose ratio. When H :glucose ratio
is low, such as 2.2:1, the total selectivity for oxidation products
2 2
O :glucose ratio on the photocatalytic oxidation
cose is decreased to 25% after five consecutive runs. The slight
reduction of photocatalytic activity maybe result from the fall
out of FePz(SBu) from the surface of H-ZSM-5 during the reaction
8
process. With respect to the selectivity of oxidation products, no
remarkable change is observed. It suggests that the H-ZSM-5/
8
FePz(SBu) material as a photocatalyst are basically stable in the
8
2 2
O
2
O
2
2 2
O
reaction of glucose oxidation.
8
Fig. 9. Reusability of H-ZSM-5/FePz(SBu) (5%) for photocatalytic oxidation of
Fig. 8. Effect of H
presence of H-ZSM-5/FePz(SBu)
2
O
2
:glucose ratio on the photocatalytic oxidation of glucose in
(5%). Reaction conditions: catalyst (30 mg), aque-
glucose in water under visible light irradiation. Reaction conditions: catalyst
ꢁ
1
8
(30 mg), aqueous glucose (3 mmol L , 30 mL), H
2
O
2
with a H
2
O
2
:glucose ratio of
ꢁ
1
ꢁ2
ous glucose (3 mmol L , 30 mL), k ꢀ 420 nm visible light (light intensity: 1.70 W
3.3:1, k ꢀ 420 nm visible light (light intensity: 1.70 W cm ), reaction for 4 h. a:
glucaric acid; b: gluconic acid; c: arabinose; d: glycerol; e: formic acid. (Note: black
bar and color bar represent the glucose conversion and product selectivity,
respectively.)
ꢁ
2
cm ), reaction for 4 h. a: glucaric acid; b: gluconic acid; c: arabinose; d: glycerol; e:
formic acid. (Note: black bar and color bar represent the glucose conversion and
product selectivity, respectively.)

R. Chen et al. / Journal of Catalysis 374 (2019) 297–305
303
3.6. Reasons for enhanced photocatalytic activity
The adsorption of substrate is generally considered to be an
important parameter in the photocatalytic process [28]. A compar-
ison of adsorption of glucose on H-ZSM-5 zeolite and H-ZSM-5/
FePz(SBu)
8
was performed, as shown in Fig. S5. It could be seen
is
that the adsorption capacity of glucose on H-ZSM-5/FePz(SBu)
8
a little higher than that of H-ZSM-5 zeolite, the increase of adsorp-
tion capacity is beneficial to the improvement of photocatalytic
activity. In addition, the transient photocurrent is usually used to
assess the charge separation efficiency in the composite photocat-
alyst [29]. In order to further illustrate the reason for the enhance-
ment of photocatalytic activity of H-ZSM-5/FePz(SBu)
transient photocurrent response versus time curves of the H-
ZSM-5/FePz(SBu) , pure H-ZSM-5 zeolite and pure FePz(SBu) were
measured under irradiation of a LED lamp emitted mainly at
20 nm in an on-and-off cycle mode, as shown in Fig. 10. From
Fig. 10, very weak photocurrent was observed in the presence of
pure H because of the possible H photolysis induced by vis-
8
, the
8
8
4
2
O
2
2 2
O
ible light. Though very weak photocurrent was also observed in
presence of H-ZSM-5 zeolite, the photocurrent value was basically
the same as that obtained in the presence of pure H O , indicating
2 2
that nearly no photocurrent was generated from the pristine H-
ZSM-5 zeolite. However, it can be seen that the H-ZSM-5/FePz
(
8
SBu) sample shows a higher photocurrent value than that of pure
FePz(SBu)
FePz(SBu)
8
, indicating that there exists a synergistic effect between
and H-ZSM-5 zeolite. The high photocurrent value of
8
8
composite H-ZSM-5/FePz(SBu) indicates a higher separation effi-
ciency of photon-generated carriers, which is favorable for the
photocatalytic activity. Therefore, it turned out that the H-ZSM-
5
/FePz(SBu)
8
will exhibit a higher photocatalytic activity compared
, which is good agree with the above
with the pure FePz(SBu)
8
results. Therefore, H-ZSM-5 zeolite not only acts as the support,
but also provides a synergistic action in the present study.
3.7. Detection of active oxygen species
In order to investigate the mechanism for the photocatalytic
oxidation of glucose to value-added chemicals over H-ZSM-5/
FePz(SBu) . The reactive oxygen species generated from H-ZSM-
/FePz(SBu) in the photocatalytic process were detected by means
8
5
8
of ESR technology and scavenger experiments. Fig. 11 shows the
ESR signals of active oxygen species generated from H-ZSM-5/
8
FePz(SBu) photocatalytic system. 5,5-dimethyl-1-pyrroline-N-
oxide (DMPO) was used as spin trap for capturing superoxide anion
ꢁ
Å
Å
1
Fig. 11. ESR signals of DMPO-O
2
adduct (A), DMPO- OH adduct (B) and TEMP- O
2
adduct (C) over H-ZSM-5/FePz(SBu)
8
(5%) under k ꢀ 420 nm visible light irradiation
1
Å
for 12 min. ESR signals of
O
2
and HO were detected in aqueous solution, while the
Åꢁ
ESR signals of O
2
were detected in methanol solution.
Åꢁ
Å
radical (O
2
) and hydroxyl radicals ( OH), and 2,2,6,6-tetramethyl
1
piperidine (TEMP) was used to detect the singlet oxygen ( O
2
).
According to the characteristic for the spin adduct, it could be seen
Åꢁ
Å
1
that strong signals of O
of H-ZSM-5/FePz(SBu)
as nickel (II) complex of glycylglycyl-l-histidine, can react with
2
, OH and O
2
are detected in the presence
8
. It was reported that metal complex, such
Åꢁ
Å
1
Fig. 10. The transient photocurrent density response of pure H-ZSM-5 zeolite, pure
FePz(SBu) and H-ZSM-5/FePz(SBu) (5%).
8 8
hydrogen peroxide to produce O
scavenger experiments were conducted by using various
, OH and O [30]. Further, the
2 2

3
04
R. Chen et al. / Journal of Catalysis 374 (2019) 297–305
8
Scheme 1. The plausible reaction routes for photocatalytic oxidation of aqueous glucose with H-ZSM-5/FePz(SBu) .
scavengers, such as 2,2,6,6-tetramethylpiperidine-1-oxyl radical
acid could be obtained from the photocatalytic oxidation of glucose
in water. Apart from these five products in the HPLC-MS analysis,
glucuronic acid was also detected, as shown in Fig. S8. But it was
not detected in the HPLC analysis, maybe owing to its very low
content. In order to expound the pathway of oxidation of glucose,
a series of experiments using glucuronic acid, glucaric acid and glu-
conic acid as substrates were further carried out in presence of H-
Åꢁ
Å
(
TEMPO) as O
2
scavenger, isopropanol (IPA) as OH scavenger
1
and b-carotene as O
2
scavenger. A procedure for scavenger exper-
iments was described in detail in the Supporting Information. As
shown in Fig. S6, it could be seen that all three scavengers exhibit
inhibitory effect on the photocatalytic oxidation of glucose. The
dramatic decline of glucose conversion was observed in the pres-
Åꢁ
Å
ence of TEMPO and IPA, suggesting that O
2
and OH are the main
8
ZSM-5/FePz(SBu) (5%) under visible light irradiation. It was found
active oxygen species dominated the photocatalytic reaction. The
that glucuronic acid could be oxidized to glucaric acid through the
HPLC-MS analysis of the oxidation products of glucuronic acid,
indicating that glucuronic acid may be an intermediate product
for the photocatalytic oxidation of glucose and the formed glu-
curonic acid could be subsequently transformed into glucaric acid
by the reactive oxygen species. Meanwhile, oxidation of glucaric
acid could produce arabinose, glycerol and formic acid through
the HPLC-MS analysis of the oxidation products. It is noteworthy
that oxidation of gluconic acid could also produce glucaric acid
Åꢁ
Å
O
2
and OH could be stabilized in the pores of H-ZSM-5 zeolite,
which consequently benefits the photocatalytic oxidation of glu-
cose. In addition, b-carotene exhibited a moderate inhibitory effect
1
on the photocatalytic process, indicating that O
2
is also the active
oxygen species in the H-ZSM-5/FePz(SBu)
8
catalytic system. These
results are good consistent with the results of ESR.
3.8. Possible reaction pathways
(Fig. S9). It suggests that the glucaric acid is produced by two ways,
one is the oxidation of glucuronic acid and the other is the oxida-
tion of gluconic acid. Therefore, the possible process pathways
In order to explore the reaction pathways for glucose oxidation,
the distribution of products as a function of reaction time was
investigated over H-ZSM-5/FePz(SBu) under visible light irradia-
(Scheme 1) are as follows: Firstly, the reactive oxygen species gen-
8
erated in the photocatalytic process can attack the C1 and C6
atoms of glucose to produce the gluconic acid and glucuronic acid.
Then, a further oxidative attack to the obtained gluconic acid mole-
cule and glucuronic acid molecule releases glucaric acid, and in
turn, glucaric acid molecule can be transformed into other prod-
ucts by an oxidative attack, such as arabinose, glycerol and formic
acid, and so on.
tion. As illustrated in Fig. S7, the glucose conversion increases with
the extension of reaction time, which is up to 67% after reaction for
6
h. But no significantly improved glucose conversion is observed
after reaction for 8 h, maybe because the oxidant H is almost
completely consumed and the glucose conversion is very low in
the case of O (Table 1, Entry 7). In the initial stage, five products
2 2
O
2
such as glucaric acid, gluconic acid, arabinose, glycerol and formic
acid are obtained, the total selectivity reaches up to 90.3%. For glu-
caric acid, gluconic acid and arabinose, their selectivity gradually
increases firstly and then remarkably gradually decreases with
reaction time, and the maximum selectivity is obtained over 4 h.
Especially, the total selectivity for glucaric acid and gluconic acid
reaches up to 45% over 4 h. While as for glycerol and formic acid,
both have the maximum selectivity at the beginning of the reac-
tion, then a remarkable reduction of selectivity is observed in com-
parison to the initial value although the selectivity don’t change
when the reaction time exceeds 2 h.
4. Conclusions
In conclusion, a new complex iron tetra(2,3-bis(butylthio)mal
eonitrile)porphyrazine (FePz(SBu) ) was successfully synthesized.
8
This work further showed that visible light (k ꢀ 420 nm) can be
used to transform glucose in water to value-added chemicals such
as glucaric acid, gluconic acid, arabinose, glycerol and formic acid
8 2 2
in presence of H-ZSM-5/FePz(SBu) photocatalysts using H O as
oxidant. It is noteworthy that the total selectivity for glucaric acid
and gluconic acid reaches up to 45% with moderate conversion of
glucose (about 35.8%) after 4 h visible light irradiation, when the
On the basis of the above analysis, five oxidation products con-
taining glucaric acid, gluconic acid, arabinose, glycerol and formic

R. Chen et al. / Journal of Catalysis 374 (2019) 297–305
305
concentration of aqueous glucose is 3 mmol L 1 and H
ratio is 3.3:1. The high photocatalytic activity of H-ZSM-5/FePz
SBu) is mainly due to the synergistic effect between FePz(SBu)
and H-ZSM-5 zeolite. With the assistance of reactive oxygen spe-
ꢁ
2 2
O :glucose
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