An Iron Oxychloride/Reduced Graphene Oxide Heterojunction with Enhanced Catalytic Performance as a Photo-Fenton Catalyst

Article abstract of DOI:10.1002/ejic.201800180

To aid with the environmental crisis, a new iron oxychloride/reduced graphene oxide (FeOCl/rGO) heterojunction has been successfully synthesized. The heterojunction shows enhanced photo-Fenton catalytic activity and stability relative to those of FeOCl under mild conditions (neutral solution and natural light). The surface area, optical adsorption, and electronegativity of FeOCl/rGO are larger than those of FeOCl, and these properties contribute to the enhanced catalytic performance of FeOCl/rGO. Furthermore, the rapid transfer of photogenerated electrons from rGO to FeOCl promotes the reduction of Fe^III to Fe^II, which boosts the production of ^·OH radicals. On the basis of active-species trapping experiments, the ^·OH radicals play a primary role, whereas ^·O₂^– radicals play a secondary role. This work demonstrates the first example of the facilitation of Fenton catalytic performance through the introduction of rGO to FeOCl for sunlight-induced photodegradation.

Full text of DOI:10.1002/ejic.201800180

A Journal of
Accepted Article
Title: FeOCl/rGO heterojunction with enhanced catalytic performance
as a photo-Fenton catalyst
Authors: Jian Zhang, Xinfu Zhao, Mingliang Zhong, Mengxue Yang, Ye
Lian, Guodong Liu, and Shaojie Liu
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201800180
Link to VoR: http://dx.doi.org/10.1002/ejic.201800180

European Journal of Inorganic Chemistry
10.1002/ejic.201800180
FULL PAPER
FeOCl/rGO heterojunction with enhanced catalytic performance
as a photo-Fenton catalyst
Jian Zhang, * Xinfu Zhao, Mingliang Zhong, [a] Mengxue Yang, [a] Ye Lian, [a] Guodong Liu * and
[
a]
[b]
[a]
Shaojie Liu [c]
[
7-11]
Abstract: In order to deal with environmental crisis effectively, a novel
FeOCl/rGO heterojunction has been successfully synthesized for the
first time, which shows enhanced photo-Fenton catalytic activity and
stability than FeOCl under mild conditions (neutral solution and
natural light). All of the surface area, optical adsorption and
electronegativity of FeOCl/rGO are bigger than that of FeOCl, which
contributes to the enhanced catalytic performance of FeOCl/rGO.
Furthermore, the rapid transfer of photogenerated electrons from rGO
Fenton catalysts.
Unfortunately, the sluggish reduction
kinetics of FeIII to Fe greatly limit its application, which becomes
II
the main challenge in heterogeneous Fenton reaction. In order to
III
improve the reduction reaction, Fe -based composites have been
explored, which however, are used under rigorous conditions
(
such as acidic solution, ultraviolet light, visible light, high
temperature or electrical energy). [12-23]
Among the heterogeneous Fenton catalysts, the FeOCl-
III
II
to FeOCl promotes the reduction of Fe to Fe , which further boosts
2
based catalysts (FeOCl, FeOCl/SBA-15 and FeOCl/SiO ) have
the production of ·OH radicals. The ·OH radicals play a primary role
shown excellent catalytic performance in degradation of organic
pollutants. [24-26] In this aspect, two kinds of two-dimensional
FeOCl and FeOCl/iron hydroxides nanosheets have been
successfully prepared by our group, which show outstanding
catalytic performance in Fenton reaction under room temperature,
neutral solution and visible light. [27-28] However, the composite
materials with FeOCl in the FeOCl-based composites mainly act
as the carrier rather than semiconductor. Reduced graphene
oxide (rGO) nanosheets are an excellent precursor for
immobilization of semiconductor to enhance the catalytic
-
while the ·O
2
radicals play a secondary role over FeOCl/rGO by the
active species trapping experiments. This work demonstrates the first
example of facilitating Fenton catalytic performance via introduction
of rGO to FeOCl for sunlight-induced photodegradation.
Introduction
In recent years, the utilization of efficient catalyst and
renewable energy to solve environmental crisis without causing
[
1-3]
second pollution has become an effective solution.
The
3 4 2 3
performance, such as Fe O /rGO, Fe O /rGO, FeOOH/rGO etc.
research enthusiasm for Fenton reaction has never declined
because it is safe, high efficient, economical and environmentally
friendly, etc. [4-6] To avoid the production of iron sludge in
[29-35]
Great efforts have been made on the electrical conductivity
of rGO in Fenton reaction, but the semiconductor characteristic of
rGO is often neglected in photo-Fenton reaction. As
a
II
homogeneous Fenton reaction (Fe -H
2
O
2
), great efforts have
photocatalyst, the narrow band gap of FeOCl leads to low
separation efficiency of electron-hole pairs. Constructing a
heterojunction structure between rGO as electron donor and hole
receptor and FeOCl maybe an effective way to accelerate the
reduction of FeIII into Fe . In addition, the band-gap of rGO is
tunable depending on its reduction level. [28-29] Therefore, the
realization of high separation efficiency of electron-hole pairs of
FeOCl may be achieved by introducing rGO into FeOCl with
matching valence band and conduction band positions.
III
been focused on the heterogeneous Fenton reaction (Fe -H
2
O
2
).
III
A series of Fe -based compounds (such as Fe
2
O
3
, FeOOH,
3 4
Fe O , Fe-MOF, etc) have been studied as heterogeneous
II
[
[
[
a]
Jian Zhang, Mingliang Zhong, Mengxue Yang, Ye Lian, Guodong
Liu
Department of chemistry and chemical engineering, Jining
University, Qufu 273100, P. R. China
E-mail: sduchemzhang@163.com
b]
c]
Xinfu Zhao
Based on the above considerations, we present a possible
solution to these challenges with formed heterojunction of FeOCl
and rGO for the first time, which effectively enhanced the catalytic
activity and structure stability of FeOCl in organic dye degradation
under mild conditions (neutral solution and natural light). The rGO
in FeOCl/rGO enhances the electron transfer and the production
Shandong provincial key laboratory for special silicone-containing
materials, Advanced materials institute, QiLu University of
Technology (Shandong Academy of Sciences), Jinan 250100, P. R.
China
Shaojie Liu
Department of chemistry and chemical engineering, Shandong
University, Jinan 250100, P. R. China
Supporting information for this article is given via a link at the end of
the document. ((Please delete this text if not appropriate))
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European Journal of Inorganic Chemistry
10.1002/ejic.201800180
FULL PAPER
of superoxide radical than FeOCl. The matching valence band
and conduction band positions of FeOCl and rGO promote the
efficient separation of photogenerated electron-hole pairs. A
synergistic mechanism for the improved catalytic performance of
Fenton reaction was elucidated.
The SEM and TEM images indicate that the morphology of
FeOCl/rGO is plate-shaped piled up by nanosheets (Fig.1c and
Fig.S1a). The corresponding EDS spectrum of FeOCl/rGO shows
that the heterojunction includes Fe, O, Cl and C elements
(Fig.S1b). Furthermore, the corresponding EDS elemental
mapping images show the even distribution of each element (Fe,
O, Cl and C, Fig.1d-g), resulting in enough contact area of FeOCl
and rGO. The results from the ultraviolet-visible diffusive
reflectance measurement (Fig.1h) indicate that the optical
absorption of FeOCl/rGO is better than that of FeOCl. Moreover,
the FeOCl/GO also favors better optical adsorption than FeOCl,
which is due to the contribution of GO in FeOCl/GO (Fig.S1b).
The optical adsorption can be further improved by the transition
of FeOCl/GO to FeOCl/rGO (Fig.S1c). According to the literatures,
Results and Discussion
3.1 characterization of FeOCl/rGO heterojunction
[
38-40]
the rGO has better optical absorption than GO. Therefore,
the transition of GO to rGO enahnces the optical adsorption of
FeOCl/rGO heterojunction, which can increase the utilization rate
of sunlight. In addition, the band gap of FeOCl/rGO decreases
compared with FeOCl, which is proved by the redshift of the
absorption edge, suggesting the enhanced conductivity and
charge separation of FeOCl/rGO.
Figure 1. (a) Schematic illustration of the synthesis of FeOCl/rGO
b) XRD pattern and (c) SEM image of FeOCl/rGO, the elemental
mapping images of (d) Fe, (e) O, (f) Cl and (g) C in FeOCl/rGO,
h) Ultraviolet-visible diffusive reflectance spectra of FeOCl and
FeOCl/rGO
The FeOCl was obtained by calcining FeCl
for an hour. Then, the NaBH solution (1 mg/mL) as reductant was
(
(
o
3
2 2
⸱6H O at 230 C
4
added to the suspension of FeOCl and GO (Fig.1a). The
FeOCl/rGO was obtained by high-speed centrifugation at 10000
r/min for 20 min. We first carried out the X-ray diffraction (XRD)
measurement to determine the crystallographic structure of
FeOCl/rGO heterojunction (Fig.1b), which shows that the obvious
diffraction peaks of FeOCl/rGO are in agreement with the pure
phase of FeOCl (orthorhombic lattice, JCPDS, No. 24-1005).
There is no appearance of characteristic peaks of rGO in XRD
pattern because of its lower content (5 wt% of rGO in FeOCl/rGO).
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European Journal of Inorganic Chemistry
10.1002/ejic.201800180
FULL PAPER
Figure 2. (a) FTIR spectrum of FeOCl/rGO, Raman spectrums of
not obvious, suggesting the weak reduction interaction of NaBH
4
(
b) FeOCl and FeOCl/rGO, (c) FeOCl/GO and FeOCl/rGO, XPS
to FeOCl. The peaks of binding energy centered at 284.5 eV and
288.7 eV correspond to C-C and C-O, respectively (Fig.2f). The
disappeared characteristic peaks of C=O and O-C=O indicate the
presence of rGO. [45-47] The reduction state of rGO is in favor of
the transfer of electrons.
spectrums of (d) FeOCl/rGO, (e) Fe 2p in FeOCl and FeOCl/rGO,
(
f) C 1s in FeOCl/rGO.
In order to further study the detail structure of FeOCl/rGO
heterojunction, the Fourier transform infrared spectroscopy
FTIR) was measured (Fig.2a and Fig.S2a-c). The FT-IR
(
3.2 Enhanced Fenton catalytic performance
-
1
spectrum of GO reveals the presence of C=O (1690 cm ), C-O
So far, the development of heterogeneous Fenton catalysts
used under mild conditions (neutral solution and nature light) is a
great challenge. Therefore, the mild conditions are adopted in our
experiment. In addition, the catalytic performance of the
FeOCl/rGO was studied by degradation of Rhodamine B (RhB),
which is a representative of organic pollutants.
-1
-1
-1
(
(
1082 cm ), C-O-C (1230 cm ) and C=C (1377 cm ) groups
Fig.S2a). The typical functional groups of GO and Fe-O (635 cm-
1)
are also observed in the FeOCl/GO (Fig. S2b). The obviously
reduced characteristic peak intensities of C=O and C-O-C of
FeOCl/rGO in Fig.2a indicate the reduction of carboxyl groups on
graphene oxide surface.[41-43] Compared with the FeOCl (Fig.S2c),
the characteristic peaks of rGO and FeOCl appeare in the FTIR
spectrum of FeOCl/rGO. The enhanced peak intensity of C-O in
FeOCl/rGO may be caused by the residual C-O group on rGO
surface and the increased interaction between rGO and FeOCl.
-
+
Due to the weak interaction between Cl and FeO in FeOCl, the
-
[
2
4
,
2
7
]
C
l
o
n
F
e
O
C
l
s
u
r
f
a
c
e
i
s
p
a
r
t
i
a
l
l
y
l
o
s
t
i
n
a
q
u
e
o
u
s
s
o
l
u
t
i
o
n
,
resulting in the electrostatic attraction between FeO+ and rGO.
The adsorption peak at 330 cm-1 in Raman spectrum is assigned
to the vibration of Fe-O group in FeOCl (Fig.2b). The distinct
Raman peak at 660 cm-1 is ascribed to the characteristic peak of
FeOCl (Fig.2b). The Raman spectrum of FeOCl/GO displays a D-
band at 1341 cm-1 and a broad G-band at 1590 cm-1 (Fig.2c),
which shift to 1352 cm-1 and 1590 cm-1 in FeOCl/rGO (Fig.2c).
Figure 3. (a) Catalytic degradation and (b) the corresponding
kinetic plots over FeOCl, FeOCl/GO and FeOCl/rGO
We first investigated the photo-Fenton catalytic activity of
FeOCl, FeOCl/GO and FeOCl/rGO (Fig.3a), which shows that the
degradation of RhB has been completed over FeOCl/rGO after 20
minutes, while reaches 88% and 64% over FeOCl/GO and FeOCl
D G
The bigger value of I /I (1.16) of FeOCl/GO than that of GO (1.10, respectively. It is obviously that the catalytic activity of FeOCl/rGO
Fig.S2d) could be accounted for the introduction of FeOCl, which
caused the increase of defects and disorders in GO nanosheets.
is the best among the three samples. Meanwhile, the
corresponding kinetic plots of FeOCl, FeOCl/GO and FeOCl/rGO
(1.25) and the 2D-band at 2700 cm-1 of
(Fig.3b) show a good linearity (R =0.98 for FeOCl, R =0.97 for
2
2
The bigger value of I
D
/I
G
2
FeOCl/rGO than FeOCl/GO (1.16) indicate the reduction of GO to
rGO. [44] To verify the chemical state, we further investigated the
FeOCl and FeOCl/rGO by X-ray photoelectron spectroscopy
FeOCl/GO and R =0.95 for FeOCl/rGO), confirming the role of the
first-order kinetic model in the catalytic reaction. The rate
constants (k) are 0.05 min , 0.10 min and 0.17 min-1 for FeOCl,
FeOCl/GO and FeOCl/rGO (Table 1), respectively. In order to
study the effect of the ratio between FeOCl and rGO on the
catalytic property, the catalytic degradation activity over different
content of rGO in FeOCl/rGO was measured (Fig.S3a), which
reveals that the 5 wt% of rGO in FeOCl/rGO is the optimal
condition. The FeOCl in FeOCl/rGO plays a major role in the
catalytic process due to the low content of rGO in FeOCl/rGO.
The effect of the reduction degree of rGO in FeOCl/rGO on
catalytic activity was also studied (Fig.S3b), which indicates that
the catalytic activity increases with the prolongation of the
-1
-1
(
XPS) analysis (Fig.2d-f). The full-range XPS spectrum of
FeOCl/rGO in Fig.2d clearly shows the signals of photoelectron
peaks of Fe, O, Cl and C, which further verifies the coexistence of
FeOCl and rGO in the heterojunction. The peaks of binding
energy centered at 711.44 eV and 725.32 eV correspond to
Fe2p3/2 and Fe2p1/2 of FeOCl respectively (Fig.2e), which reveals
the FeIII state in FeOCl. The peaks of Fe2p3/2 and Fe2p1/2 shifted
to a higher degree in FeOCl/rGO than that in FeOCl (Fig.2e),
which is caused by the interaction between FeOCl and rGO.
However, the change of peak of Fe in FeOCl/rGO and FeOCl is
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European Journal of Inorganic Chemistry
10.1002/ejic.201800180
FULL PAPER
reduction time. However, there is little difference of the reduction
time between 20 min and 30 min in catalytic activities. Therefore,
the FeOCl/rGO sample with the reduction time of 20 min was
adopted in our experiments. Considering the practical application,
it is noteworthy that the stability is also an important aspect.
Hence, we studied the catalytic stability of FeOCl/rGO by cycling
degradation experiments. The recovered catalyst is collected
after each run by high-speed centrifugation at 10000 r/min for 30
min and dried to be ready for the next run. It is to be noted that all
the cycling degradation testing runs were performed under the
same operating conditions (Fig.S4). The results show that the
FeOCl/rGO has excellent stability in the cycling degradation
experiments. The degradation rate reaches 97% in the fourth
cycling runs. Furthermore, the XRD pattern of FeOCl/rGO after
catalytic process in Fig.S5 indicates the unchanged phase
structure of FeOCl/rGO. The low iron leaching (1.37 ppm) does
not cause secondary pollution to the water. The pH value
decreases to 6.5 after recycling runs, which is mainly caused by
the acidity of hydrogen peroxide. Thus, we can draw the
conclusion that the rGO does improve the structure stability of
FeOCl in the photo-Fenton reaction.
Figure 4. N
2
adsorption-desorption isotherms of (a) FeOCl and
(b) FeOCl/rGO, (c) mean pore diameter and (d) pore volume of
FeOCl and FeOCl/rGO
To further study the contribution of rGO in FeOCl/rGO, the
Brunauer-Emmett-Teller (BET) measurement was carried out
(Fig.4), which shows that the surface areas of FeOCl and
2
2
FeOCl/rGO are 2.48 m /g and 13.58 m /g, respectively (Fig.4a-b).
The presence of rGO greatly increases the surface area of
FeOCl/rGO, which is five times as many as that of FeOCl. The
2
surface area of FeOCl/GO was also measured (11.79 m /g,
Fig.S6), which is smaller than that of FeOCl/rGO, suggesting that
the reduction of GO to rGO promotes the increase of surface area
of FeOCl/rGO. Furthermore, the mean pore diameter and pore
volume of FeOCl/rGO are bigger than that of FeOCl (Fig.4c-d).
2
We further measured the N adsorption-desorption isotherms of
rGO (Fig.S7), which indicates that the surface area of rGO is
2
319.20 m /g and the mean pore diameter is 4.60 nm. The mean
pore diameter of rGO is smaller than that of FeOCl/rGO (10.06
nm), suggesting that the increased mean pore dimieter is mainly
caused by FeOCl (8.11 nm). There are many structural defects
with high activity in FeOCl, which further increased by the etching
2
Table 1. the rate constants (k) and regression coefficients (R ) of
4
of NaBH . The bigger surface area of FeOCl/rGO can provide
photo-Fenton catalytic degradation over FeOCl, FeOCl/GO and
FeOCl/rGO
more active sites and bigger adsorption amount of organic
contaminant than that of FeOCl, indicating the promotive action
to catalytic performance.
-1
R2
Catalyst
k (min )
FeOCl
0.05
0.98
0.97
0.95
FeOCl/GO
FeOCl/rGO
0.10
0.17
3.3 Mechanism for enhanced catalytic performance
Figure 5. (a) The catalytic degradation with the same total surface
area and (b) the adsorption under darkness over FeOCl,
FeOCl/GO and FeOCl/rGO
The adsorption of organic pollutant on catalyst surface is
crucial to catalytic activity, owing to the very short life and
transmission distance of active species (·OH and ·O
2
H radical)
produced by the catalyst and H
2
O
2
. [48-50] To study the effect of
surface area on catalytic activity, we further measured the
catalytic activities over FeOCl, FeOCl/GO and FeOCl/rGO with
2
the same total surface area (0.68 m , Fig.5a and Fig.S6), which
were carried out by increasing the weights of FeOCl and
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European Journal of Inorganic Chemistry
10.1002/ejic.201800180
FULL PAPER
FeOCl/GO to 0.27g and 0.06 g from 0.05 g, respectively. Notably,
the degradation rates over FeOCl and FeOCl/GO increase when
they are of the same total surface area as FeOCl/rGO (Fig.3a),
implying that the surface area is helpful to the improvement of
catalytic activity. However, the catalytic activities over FeOCl and
FeOCl/GO are still lower than that over FeOCl/rGO. The
corresponding kinetic plots of catalysts (Fig.S8 and Table S1)
show that the FeOCl/rGO is the best among the three samples.
Thus, together with the results from Fig.3a-b, the enhanced
catalytic degradation activity over FeOCl/rGO is partly due to the
increased surface area. Furthermore, the better catalytic activity
of FeOCl/rGO than FeOCl/GO is perhaps due to the better
conductivity of rGO than that of GO.
Figure 6. (a) Photoluminescence spectra and (b) electrochemical
impedance spectra (Nyquist plot) of FeOCl, FeOCl/GO and
FeOCl/rGO.
In order to verify the high separation efficiency of charge pairs
over FeOCl/rGO, the photoluminescence (PL) spectrum
In addition, the effect of surface area on catalytic activity is
also reflected in the adsorption of RhB. To further study the effect
of adsorption of RhB on catalyst surface, we measured the
adsorption of RhB on FeOCl, FeOCl/GO and FeOCl/rGO under
darkness (Fig.5b), which shows that the adsorption on FeOCl is
very weak (just reach 7% after 60 min) while it increases to 21%
on FeOCl/GO and further increases to 25% on FeOCl/rGO. The
strongest adsorption of FeOCl/rGO towards organic dyes among
them can effectively decrease the transmission distance of active
species and thus promote the catalytic activity. Although the
difference in the adsorption of RhB on FeOCl/GO and FeOCl/rGO
is small (4%), the catalytic activity of FeOCl/rGO is much better
than that of FeOCl/GO, which implies that the main contribution
of rGO is to improve the separation efficiency of photogenerated
electron-hole pairs.
measurement was carried out (Fig.6a). The high separation
efficiency can be revealed by low PL emission intensity. [51] The
PL emission intensity of FeOCl/GO is weaker than that of FeOCl
(
Fig.6a), implying that the FeOCl/GO effectively increases the
separation efficiency. Furthermore, the PL emission intensity of
FeOCl/rGO is even weaker than that of FeOCl/GO, which
indicates that the combination of FeOCl with rGO further improves
the separation efficiency. The formed strong interaction between
FeOCl and rGO improves the interfacial electronic transmission
in high efficiency for photo-generated electrons. The
electrochemical impedance spectroscopy (EIS) is an effective tool
for the investigation of the charge transfer process, which was
further measured to study the charge transfer on the interfacial
contact (Fig.6b). In general, the small radius of the Nyquist circle
reveals the low charge-transfer resistance. [52] The arc radius of
In addition, the surface potential also has an effect on the
surface adsorption. Therefore, we also measured the surface
potentials of FeOCl, FeOCl/GO and FeOCl/rGO, suggesting that
the zeta potentials of FeOCl, FeOCl/GO and FeOCl/rGO are -
the FeOCl/rGO is the smallest among the three samples,
demonstrating the fastest interfacial charge transfer and the
highest separation efficient of photo-generated charge carriers in
FeOCl/rGO.
30.02 mV, -46.82 mV and -42.21 mV, respectively. The reason for
the decreased electronegativity of FeOCl/rGO than FeOCl/GO is
the reduction of graphene oxide. Furthermore, the
electronegativity of FeOCl/rGO can effectively increase the
repulsion between particles and the dispersion of suspension.
Although the electronegativity of FeOCl/GO is stronger than that
of FeOCl/rGO, the adsorption amount order of RhB on them are
opposite (Fig.5b), which indicates that the surface area plays a
major role in the adsorption of organic pollutant, while the surface
potential plays a secondary role.
Figure 7. Charge density of (a) FeOCl and (b) FeOCl/rGO. The
isosurface level is 0.2.
To further study the interaction between FeOCl and rGO, we
also calculated the interaction between them (Fig.7a-b). The
Hirshfeld charge of Fe in FeOCl was 0.14 (Fig.7a) and decreased
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European Journal of Inorganic Chemistry
10.1002/ejic.201800180
FULL PAPER
to 0.13 after combination with rGO (Fig.7b), which indicates that
the chemical valence of iron atoms in FeOCl is partially reduced
due to the combination of rGO and FeOCl. The bond order of Fe-
Cl in FeOCl is 0.35 while it increases to 0.37 in FeOCl/rGO, which
implies the increased interaction of Fe-Cl in FeOCl/rGO. Besides,
the decreased bong length of Fe-Cl in FeOCl/rGO (2.18 Å)
compared with that in FeOCl (2.22 Å) also indicates the increased
interaction of Fe-Cl. On consideration of the loss of Cl atoms in
FeOCl surface in water due to the weak interaction of Fe-Cl, the
increased interaction of Fe-Cl can effectively improve the
structure stability of FeOCl/rGO.
The introduction of IPA has an obvious effect on the photo-Fenton
catalytic activity (Fig.8a), which shows that the degradation is
suppressed to 52% from 64% over FeOCl. The degradation is
suppressed to 48% over FeOCl/GO while it is further suppressed
to 43% from 100% over FeOCl/rGO, which indicates that the ·OH
radicals are the main reactive oxidative species involved in the
catalysis. The effect of ·OH radical on the photo-Fenton catalytic
activity gradually increase in the order of FeOCl, FeOCl/GO and
FeOCl/rGO, which implies the increased amount of ·OH radical in
2 2
turn. The decomposition of H O was measured by fluorescence
technique with terephthalic acid as trapping agent (Fig.S10),
because the terephthalic acid can react with ·OH radicals to
produce
decomposition rate reveals high production of ·OH radicals. The
decomposition is almost complete over FeOCl/rGO, which
2-hydroxyterephthalic
acid.
The high
2 2
H O
2 2
H O
is obviously better than that over FeOCl/GO and FeOCl (67%),
suggesting the contribution of rGO in promoting the
decomposition of H
2
O
2
to produce ·OH radical. According to the
the amount of ·O -
radical can reflect the
reduction of FeIII to Fe , which comes from two aspects in Fenton
reaction (the reduction of O
to ·O - radical and the reaction of FeIII
with H ).
Because the CB potential of the FeOCl (0.10 V) is positive
/·O -
than the potential of O (-0.046 V vs. NHE), the generated
·O - radicals over FeOCl are from the reaction between FeIII and
2 2
H O , which is sluggish due to the unconspicuous suppressed
[
55-56]
literatures,
2
II
Figure 8. Trapping experiments of active species of (a) ·OH and
-
(
b) ·O
2
radicals over FeOCl, FeOCl/GO and FeOCl/rGO
2
2
In order to further explain the enhanced photocatalytic
2 2
O
Fenton activity mechanism, the band edge positions of the
valence band (VB) and conduction band (CB) potentials of FeOCl
2
2
and rGO were measured. The direct optical band gaps E
g
of
2
FeOCl and rGO are 1.85 eV and 1.68 eV (Fig.1g and Fig.S9a),
which are consistent with the literatures. [26-27, 53] The position of
degradation over FeOCl (reach 61% from 64%, Fig.8b). The
degradation rates are suppressed to 82% and 91% from 88% and
100% over FeOCl/GO and FeOCl/rGO respectively (Fig.8b),
the CB is very close to the Efb. [53-54] The flat band potentials (Efb
of the FeOCl and rGO are estimated to be −0.55 eV and -0.70 eV
vs. SCE, pH = 7) in Mott-Schottky plots (Fig.S9b-c). Therefore,
)
(
indicating the increased amount of ·O -
and FeOCl/rGO than FeOCl. On one hand, the photo-generated
electrons on GO and rGO can reduce O radicals. On
to form ·O -
2
radical over FeOCl/GO
the CB potentials of the FeOCl and rGO are calculated to be 0.10
eV and -0.05 eV (vs. NHE, pH=0). According to results from
ultraviolet-visible diffusive reflectance spectra, the corresponding
VB potentials of FeOCl and rGO are 1.95 V and 1.63 eV (vs. NHE,
pH=0).
2
2
the other hand, the photo-generated electrons on GO and rGO
can also transfer to FeOCl, which leads to the reduction of FeIII to
FeII and further produces more ·O -
radicals. To examine the
2
The active species are the key in Fenton reaction, which are
effect of dissolved oxygen on the reduction of FeIII to Fe , the
II
mainly ·OH radical and ·O -
radical in heterogeneous Fenton
trapping experiment of ·O -
deaerated conditions (using N
radicals was performed under
2
sparging), and the results were
2
2
reaction. [5-6] To analyze the role each reactive specie plays in the
catalytic process, the different scavenges used as probes have
been introduced into the photo-Fenton catalysis. They were iso-
compared to those under air conditions (Fig.S11), which reveals
that the degradation rates are suppressed to 85% and 93% over
FeOCl/GO and FeOCl/rGO respectively. The bigger suppressed
degradation degree of FeOCl/GO and FeOCl/rGO than that of
propyle alcohol (IPA) for ·OH radical and benzoquinone (BQ) for
-
·
O
2
radical. If the free radical scavenger plays an important role
in the catalysis, the photo-Fenton catalytic activity would be
decreased greatly in the presence of the appropriate scavenger.
FeOCl indicates more amount of ·O -
FeOCl/rGO, revealing the photo-generated electron transfer to
2
radical over FeOCl/GO and
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European Journal of Inorganic Chemistry
10.1002/ejic.201800180
FULL PAPER
FeOCl from GO and rGO. According to the literatures, GO is a
broadband gap semiconductor. [57-60] The VB of GO is positive
than that of FeOCl. Thus, the holes in VB of GO can transfer to
FeOCl, which leads to accumulation of holes in FeOCl. Therefore,
the separation efficiency of electron-hole pair of FeOCl/GO is
lower than that of FeOCl/rGO, resulting in lower catalytic activity
of FeOCl/GO than that of FeOCl/rGO.
electroconductivity of rGO in FeOCl/rGO increases. The
photogenerated electron in FeOCl would transfer to rGO,
resulting in the decreased catalytic activity of FeOCl/rGO
(Fig.S12a-b), whih has been proved by the increased amount of
·O -
d when the reduction time is 40 min and the content of NaBH
radical and the decreased amount of ·OH radical in Fig.S12c-
is
2
4
50 mg. Based on above analysis, the reduction degree of GO in
FeOCl/rGO has great effect on the catalytic activity of FeOCl/rGO.
When the reductin degree of GO in FeOCl/rGO is small, the band
gap of rGO is big which results in low separation efficiency of
electron hole pairs. However, when the reduction degree of GO
in FeOCl/rGO is too big, the superconductivity of rGO leads to the
transfer of photogenerated electrons from FeOCl to the surface of
rGO, resulting in low catalytic activity of FeOCl/rGO. The
realization of efficient separation efficiency of electron-hole pairs
and electron transfer from rGO to FeOCl depends on the suitable
reduction degree of rGO in FeOCl/rGO.
However, the suppressed degradation by ·OH radical is
obviously better than that by ·O -
radical. Therefore, the
2
contribution of rGO is mainly to accelerate the transfer of
photogenerated electrons to FeOCl. Based on above analysis,
the ·OH radical plays a major role and the ·O -
radical takes a
2
minor role on the degradation of RhB with FeOCl/rGO. Therefore,
the oxidation mechanism of FeOCl/rGO proceeds through direct
·
OH attack to target organic compounds. The sunlight improves
the activity by promoting the photogenerated electrons
transformation and photo-reduction of FeIII into FeII in
heterogeneous photo-Fenton reactions. [61] The Fe subsequently
II
2 2
reacts with H O to generate ·OH radicals on the surface and
further to degrade organic contaminants.
The mechanism that rGO could enhance the photo-Fenton
catalysis of FeOCl is closely related to the degree of reduction of
GO. The degradation activity of FeOCl/rGO is better than that of
FeOCl/GO, indicating that the reduction of GO does enhance the
catalytic activity (Fig.3). We further measured the catalytic activity
of FeOCl/rGO with different reduction degree of GO in FeOCl/rGO
(
Fig.S12a-b). The catalytic activity of FeOCl/rGO is the best when
the reduction time is 20 min compared with 10 min and 40 min
Fig.S12a), which indicates that the reduction degree of GO in
Figure 9. Mechanistic scheme of the FeOCl/rGO for the
(
photocatalytic degradation with H O under sunlight.
2
2
FeOCl/rGO is not the bigger the better. In order to further prove
this viewpoint, the degradation activity of FeOCl/rGO with
Accordingly, the synergistic effect of FeOCl/rGO on
enhanced photo-Fenton catalytic performance is proposed. As
illustrated in Fig. 9, both FeOCl and rGO can be initiated by the
indoor-sunlight to yield photogenerated electron-hole pairs. The
photogenerated electrons in the CB of rGO can transfer quickly to
FeOCl, which leads to the accumulation of electrons in the CB of
FeOCl. The holes in VB of FeOCl can also transfer quickly to the
rGO. It can make the effective segregation of photogenerated
electron-hole pairs and more electrons available for the reduction
of FeIII into Fe , thus improves the catalysis activity under indoor-
sunlight. The accumulation of electrons in FeOCl accelerates the
reduction of FeIII into Fe , which is much more rapid than the
4
different content of NaBH was also measured (Fig.S12b), which
demonstrates that the further increased reduction degree of GO
in FeOCl/rGO is unfavorable to the improvement of catalytic
4
activity when the content of NaBH is 50 mg. Furthermore, the
trapping experiments of active species over FeOCl/rGO with
different reduction degree of GO were also carried out (Fig.S12c-
d). The effect of ·OH radical on the photo-Fenton catalytic activity
of FeOCl/rGO increases following the increase of reduction
degree of GO in FeOCl/rGO, while decreases when further
II
II
increase the reduction degree of GO in FeOCl/rGO. However, the
-
reaction of FeIII with H O2 to generate Fe . The formed Fe
II
II
effect of ·O
2
radical decreases first and then increases as the
2
increase of reduction degree of GO in FeOCl/rGO. When the
reduction degree of GO in FeOCl/rGO is big, the
2 2
subsequently reacts with H O to generate ·OH radicals on the
surface and further to degrade organic contaminants. Meanwhile,
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European Journal of Inorganic Chemistry
10.1002/ejic.201800180
FULL PAPER
the accumulation of the holes with strong oxidation in rGO can
constantly for 40 min. Then, 10 mL NaBH
4
solution (1 mg/mL) was added
in the mixture and stirred constantly for another 20 min. The obtained
product was washed with ethanol three times, and then dried at 90 oC in
vacuum oven for 12 h.
also degrade organic contaminants. Furthermore, the reaction of
FeIII with H
+
2
O
2
can also generate H , which causes the decrease
of pH value and the iron leaching. The accelerated reduction of
FeIII into FeII by the transfer of photogenerated electrons
+
effectively decrease the generation of H and further enhance the
Catalytic activity measurements
structure stability of FeOCl. In addition, the contribution of rGO in
FeOCl/rGO mainly reflected in five aspects: the increased surface
area, optical adsorption, surface electronegativity, structure
stability, rapid electron transfer and the reduction of FeIII into FeII.
All of these aspects are expected to enhance the photocatalytic
performance of FeOCl/rGO.
The Fenton catalytic performance of FeOCl/rGO was tested by the
2 2
degradation of RhB with H O at pH=7 (initial pH value of RhB solution)
under sunlight and room temperature. In a typical experiment, 0.05 g of
FeOCl/rGO composite was added into a 100 mL RhB solution (5 mg/L)
and stirred for 60 min to reach the adsorption equilibrium. The reaction
2 2
was initiated by adding 0.5 mL of H O aqueous solution (30 wt%). During
the reaction, 5 mL of the reaction mixture were taken out at certain time
interval (5 min) and centrifuged before measuring the UV-vis absorption
spectra. Besides, the Fenton reaction by using FeOCl and FeOCl/GO with
the same weight (0.05 g) was carried out as comparison. The degradation
efficiency was calculated following as equation (1):
Conclusions
In this work,
a novel FeOCl/rGO heterojunction was
successfully prepared by a facile method. The FeOCl/rGO
heterojunction shows excellent photocatalytic activity and
structure stability for organic pollutants degradation as Fenton
reagent under mild condition (neutral solution and nature light).
The FeOCl/rGO heterojunction has better optical adsorption,
bigger surface area and surface electronegativity than FeOCl.
The rGO in FeOCl/rGO strengthens electron transfer and
improves the reduction of FeIII into Fe . In the meantime, rGO in
FeOCl/rGO also promoted the production of superoxide radicals
and enhanced the structure stability of FeOCl. The FeOCl/rGO
heterojunction can shed new light on the applications of
environmental crisis.
0
η = (1-C/C ) ×100%
(1)
0
where η represents for the degradation efficiency; C and C represent
the concentration of original dye solution and after a period of irradiation,
respectively.
II
Active species trapping experiments
To investigate the main active species responsible for the photo-
Fenton catalytic reaction, the benzoquinone (BQ, 1 mM) and iso-propyle
alcohol (IPA, 1 mM) were employed as the scavengers for superoxide
Experimental Section
radical (·O -
) and hydroxyl radicals (·OH), respectively. The method was
2
like the above photocatalytic activity test.
Materials
2 2
Decomposition of H O
All of the chemicals were purchased from Sinopharm Chemical
Reagent Co., Ltd, and were of analytical grade and used without any
further purification.
2 2
The decomposition of H O on FeOCl/rGO was determined by
fluorescence technique with terephthalic acid as trapping agent. 0.05 g of
FeOCl/rGO was added to 100 mL terephthalic acid solution and stirred for
Synthesis of FeOCl/rGO heterojunction
2 2
60 min. And then, the reaction was initiated by adding 0.5 mL of H O
aqueous solution (30 wt%). During the reaction, 5.0 mL of the reaction
mixture were taken out at certain time interval (10 min) and centrifuged
before measuring the fluorescence spectrophotometer.
We used a facile method to prepare FeOCl/rGO heterojunction. The
FeOCl was synthesized using our previous work. [27] In a typical process,
0.1 g FeOCl dispersed in 50 mL GO suspension (0.1 mg/mL) and stirred
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European Journal of Inorganic Chemistry
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Characterization
Acknowledgements
This work is supported by Natural Science Foundation of
Shandong Province (ZR2016BB21), Science and technology plan
project of Shandong colleges and Universities (J17KB063) and
Talent Team Culturing Plan for Leading Disciplines of University
in Shandong Province.
The phase structure of the product was identified using XRD
o
o
technique (scan rate, 2 /min; scan step, 0.06 ) on a Rigaku D/Max 2200-
PC diffractometer with the tube electric voltage and current of 40 kV and
3
5 mA for CuKα radiation (λ=0.15418 nm) and graphite monochromator at
ambient temperature. The shape and size were characterized by TEM
JEM-100CXII) with accelerating voltage of 80 kV. The Fourier Transform
infrared (FT-IR) spectra were measured on Nicolet 5DX-FTIR
spectrometer using KBr pellet method in the range of 400~4000 cm . The
Brunauer-Emmett-Teller (BET) surface area (SBET) was measured by N
(
a
Keywords: FeOCl • rGO • Fenton • DFT
-
1
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a novel FeOCl/rGO heterojunction
has been successfully synthesized.
The rapid transfer of photogenerated
electrons from rGO to FeOCl
promotes the reduction of FeIII to FeII
and further boosts the production of
Photo-Fenton catalyst
Jian Zhang, *[a] Xinfu Zhao,
[b]
[a]
Mingliang Zhong, Mengxue Yang,
[
a]
[a]
*[a
Ye Lian, Guodong Liu ] and
Shaojie Liu [
c]
Page No. – Page No.
·
OH radicals.
Enhanced catalytic performance
using FeOCl/rGO as a photo-
Fenton-like catalyst
*one or two words that highlight the emphasis of the paper or the field of the study
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