Journal of Molecular Liquids 322 (2021) 114815

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

MOF assisted synthesis of TiO2/Au/Fe2O3 hybrids with enhanced

photocatalytic hydrogen production and simultaneous removal
of toxic phenolic compounds
Yongxia Li a,b, Binsheng Yang a, Bin Liu a,⁎
a
Institute of Molecular Science, Engineering Research Centre for Sewage Treatment Shanxi Province, Shanxi University, Taiyuan 030006, China
b
Department of Chemistry, Xinzhou Teachers University, Xinzhou 034000, China

a r t i c l e i n f o a b s t r a c t

Article history: The heterojunction photocatalyst namely TiO2/Fe2O3 modified with different Au loadings has been constructed
Received 23 September 2020 via a one-pot metal-organic framework (MOF) route which using titanium (IV) butoxide and iron nitrate as pre-
Received in revised form 9 November 2020 cursors. The characteristics studies show that the nano-shaped TiO2 is spreaded uniformly on the surface of Fe2O3
Accepted 15 November 2020
along with Au deposition. The noble Au metal acts as an electron mediator which has been enabled in enhancing
Available online 19 November 2020
the photocatalytic performances of TiO2/Fe2O3 heterojunction. The photocatalytic ability was evaluated through
Keywords:
the H2 production (using water-splitting reaction) and removal of phenolic compounds namely 2,4 dichlorophe-
Au-modified TiO2/Fe2O3 nol (2,4-DCP) and 4-bromophenol (4,B,-P) under the largely available visible light in solar spectrum. The highest
MOF assembly H2 production of 590 μmol g−1 h−1, with an apparent quantum yield of 12%, was obtained using the glycerol as
Co-catalyst sacrificial reagent using 4% Au-Fe2O3/TiO2 photocatalyst. By examining the special impact of different scavengers,
H2-evolution performance it paraded that the hydroxyl and superoxide radicals mainly participated in the photocatalysis process. The com-
Phenol compounds bined effect of TiO2 and Fe2O3 and effective Au deposition lead to an upgraded carrier separation efficiency and
outstanding photocatalytic performances. Furthermore, the close interface formed by metallic Au material point-
edly slows down the recombination of e−/h+, which is high advantageous for the photocatalytic processes using
naturally available sunlight or visible-light. This work delivers a novel perception to develop a stable noble-metal
photocatalyst material in the H2 production and the removal of phenolic compounds in the industrial areas.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction
H2 production using semiconductor materials has been recognized
as one of the eye-catching methodologies for resolving the various en-
ergy and environmental issues posed by conventional methodologies
[1–4]. TiO2 (with rutile and anatase phases) is still well-studied
photocatalyst mainly due to its less cost, chemical stability, and eco-
friendliness [5,6]. However, the pure TiO2 semiconductor establishes re-
duced photocatalytic activities due to the higher recombination of
photogenerated charge carriers. It has been previously reported that
the loading of precious metals such as silver (Ag), gold (Au), and
platinum (Pt) nanoparticles can act as excellent co-catalyst on the
TiO2 surface which can promote the separation of charges effectively
in photo-generated carriers [7,8]. Particularly, the metallic Au can
serve as smart co-catalysts to facilitate the H2 generation and degrada-
tion efficiency of the host TiO2 due to its outstanding electrical conduc-
tivity [9]. Neverthless, the photocatalytic performances of Au deposited
TiO2 is still inadequate when compared with Pt decorated TiO2 due to
⁎ Corresponding author.
E-mail address: Liubin_518@126.com (B. Liu).
the weaker bond strength and lower free energiesinbonding hydrogen
in the host TiO2 material. Therefore, it's still extremely meaningful to
progress the H2 production of Au-decorated TiO2 photocatalyst [10].
In the other hand the acceleration in industrialization development
in cities has emphasized phenolic compounds as building blocks for var-
ious polymers discharged from textile and pharma factories [11]. The
complex structure of the phenolic compounds present in water bodies
makes their degradation exceptionally difficult. The phenolic com-
pounds have a seriously negative impact on aquatic lives and the
human race [12]. Exertions have been made to remove the organic pol-
lutants by cost-effective treatment processes [13]. Thus, semiconductor
photocatalysts with capabilities to degrade the wide range of phenolic
pollutants under visible light, have been studied recent days due to
their cost-effectiveness, high efficiency, and no secondary pollutants
generated in water bodies [14]. Semiconductor photocatalysts namely,
ZnO and TiO2 have been used as commercial photocatalysts [15]. TiO2
is considered to be an important material due to its good oxidizing abil-
ity, and nontoxicity. But drawbacks of TiO2 include the fast recombina-
tion rate of excitons, poor response under solar energy, and lower
cyclability for industrial purposes. Modifying TiO2 with Fe2O3 can im-
prove the photocatalytic activity in real-time applications [16].

https://doi.org/10.1016/j.molliq.2020.114815
0167-7322/© 2020 Elsevier B.V. All rights reserved.
Y. Li, B. Yang and B. Liu
However, the heterojunctions prepared from conventional sol-gel
methods are prone to severe agglomeration, which decreases its surface
area due to vander Waals forces. The agglomerated nano-catalyst is dif-
ficult to perform the expected photocatalytic performances resulting in
great challenges to a wide range of practical applications [17–20].
Metal-organic frameworks (MOF's), are known as three dimensional
architectures with higher porosity, is considered to be an ideal candi-
date for the photocatalyst [21,22]. Great efforts have been completed
to use MOF as novel prevailing supports for the preparation of semicon-
ductor materials [23]. Recently, MOFs as sacrificial templates to
fabricate TiO2 nanostructures is gaining more attention [24]. MOFs
with abudant confined pores can form a homogeneous structure,
which promotes the electron mobility and supplies more reactive
sites. However, the incomplete visible light absorption capability of
the TiO2 prepared by MOF route has considerably limited its application
in the photocatalyst process. The synthesis of efficient MOF derived TiO2
system photocatalytic systemsis still a big challenge [25]. Therefore, a
useful technique is required to improve the visible light reactions of
TiO2 and increase its photocatalytic performance by combination with
any other catalyst which has narrow bandgap energies. In general,
Fe2O3 is well thought-out as aperfect candidate to advancethe photocat-
alytic properties of active TiO2 under UV. Furthermore, plasmonic
catalysts can also be implemented to enhance the photocatalytic perfor-
mances of rutile or anatase phase TiO2 due to the existence of SPR (sur-
face plasmon resonance effect). It is investigated that SPR catalyst can
increase the visible-light responses and restricts the quick electron-
holes recombination [26,27]. Moreover MOFs derived TiO2 and Fe2O3
nanostructures have been employed in various fields such as
photocatalysis, gas storage, biosensors and chemisorption, etc. Thus,
MOF derived TiO2 and Fe2O3 have attracted great attention owing to
its high surface area, outstanding porosity, and lower density. Many ex-
perimental reports that on the MOF derived semiconductors have
shown that these architectures can act as a outstanding photocatalysts
under visible irradiation.
In this present work, we have successfully prepared the TiO2/Au/
Fe2O3 hybrids with a hierarchical structure via a simple metal organic
framework assisted (MOF) method. The synthesized composite was ap-
plied to the photo-degradation of two phenolic compounds namely 2,4
dichlorophenol (2,4-DCP) and 4-bromophenol (4-B,P) respectively. The
Au-TiO2/Fe2O3 catalyst prepared by the MOF assisted route exhibited
wide light response range the reduced the agglomeration effect and
high recyclablity. The Au-TiO2/Fe2O3composite is an excellent outlook
for extensive applications in wastewater treatment and energy sector.
2. Experimental section
2.1. Materials
Tetrabutyl Titanate (Ti(C4H9O)4), N, N-dimethylformamide (DMF),
methanol, ferric nitrate nonahydrate (Fe(NO3)3·9H2O), and chloroauric
acid (HAuCl4), have been procured from Shanghai Sinopharm Chemical
company from China. Terephthalic acid (benzene dicarboxylic acid
(H2BDC) and glycerol was obtained from Sigma Aldrich. All obtained re-
agents were AR purity and directly used and no purification process has
been done. Tetrahydrofuran (THF) was purchased from Merck. Deion-
ized water (DI) and ethanol (anhydrous) was used in all experimental
studies.
2.2. Synthesis of the TiO2/Au/Fe2O3 composites
2.2.1. Synthesis of Ti-Fe-MOF
Fe (NO3)3·9H2O (2 mmol), and Ti (C4H9O)4 (2 mmol) was mixed
with 40 mL of DMF and 5 ml methanol and stirred at 30 °C for 20 min
and the yellow color mixture was named as solution A. The powderred
form of terephthalic acid (2 mmol) was mixed with 20 mL of DMF and
constantly stirred using magnetic stirrer at room temperature for
2
Journal of Molecular Liquids 322 (2021) 114815
60 min, and it can be referred as solution B. Then, solution A was trans-
ferred into solution B, and it was allowed to stir for an additional 60 min.
Finally, the homogeneous mixture was transferred into a 75 mL Teflon
lined autoclave, and kept at a temperature of 160 °C in a muffle furnace
for 10 h at air atmosphere. Afterward, the mixture was naturally cooled
and the solution was washed thoroughly with ethanol, THF, and finally
dehydrated at vacuum at 80 °C overnight to get a brown powder.
2.2.2. Synthesis of TiO2/Au/Fe2O3 composites
The synthesized Ti-Fe-MOF (0.150 g) was dispersed in 30 mL of
chloroauric acid (HAuCl4) with the help of ultrasonication and the
amount of HAuCl4 in water was varied. After it was completely dis-
persed, the suspension was transferred to a 70 mL Teflon lined auto-
clave and treated at 120 °C for 6 h. After the product was cooled, the
pale brown precipitate was heated at 400 °C under air atmosphere for
3 h to obtain a TiO2/Au/Fe2O3 nanocomposite. Five products were syn-
thesized via the same method, TiO2/Au/Fe2O3 (0.5%), TiO2/Au/Fe2O3
(2%), TiO2/Au/Fe2O3 (3%), TiO2/Au/Fe2O3 (4%) and TiO2/Au/Fe2O3 (5%),
according to the weight percentage of Au loadings.
2.3. Characterization studies
The p-XRD (powder X-ray diffraction) characterizations of the TiO2/
Fe2O3, and TiO2/Au/Fe2O3 nanocomposite were recorded under the am-
bient atmosphere by a Rigaku X-ray diffractometer. The measurements
were performed under Cu-Kα irradiation (λ = 0.154 nm) with a aver-
age scanning rate of 5° min−1 at 2θ values from the 2 theta 10 to 80°.
The morphological features and structural properties of the TiO2/Au/
Fe2O3 nanocomposite were executed by a high beam scanning electron
(field-emission) microscope using, SIGMA HV-Carl Zeiss fitted with
EDS detector manufactured by Bruker Quantax Z10 model) and
transmission electron images were analyzed by a JEOL JEM-1230 micro-
scope. XPS-ESCA (X-ray photoelectron spectra) was recorded by
Omicron GMBH instrument system fitted with Al-Kα irradiation. The
photoluminescence (PL) spectra were recorded on a HORIBA spectrom-
eter with a laser excitation of 300 nm. To evaluate the chemical states,
the binding energy of all elements has been standardized using the
C1s spectrum observed at 284.6 eV. UV–vis DRS (diffuse reflectance
spectra) were recorded on a Jasco, V-750 UV–vis spectrophotometer
in the wavelength ranges from 200 to 800 nm using BaSO4 as an internal
standard. The EIS spectra of the samples were documented over the fre-
quency range from 100 Hz to 0.01 Hz using Autolab instrument using a
conventional three-electrode system.
2.4. Photodegradation of 2,4-DCP and 4-BP
Photo-degradation of 2,4-DCP, and 4-BP was performed in the batch
process under visible light illumination. A sodium lamp with a maxi-
mum intensity of 200 W Philips was employed as the visible light
source. To avoid heating, the lamp was covered by a water-cooler fitted
with a condenser. The prepared photocatalyst was mixed to the
2, 4-DCP, and 4-BP standard solution (10 mg−1). To ensure the
adsorption-desorption equilibrium between pollutants and the cata-
lysts, the mixture was stirred continously continuously in the dark
and then the mixture was illumination under the visible light. During
the degradation process, the remnant concentration of the 2, 4 DCP,
and 4-BP solutions was measured at various time intervals. The final ab-
sorption as concentrations i.e. Ct of the 2, 4-DCP and 4-BP in the solution
was deliberate by using standard curve method. The degradation effi-
ciency of the TiO2/Au/Fe2O3 samples was calculated as follows,
C/C0% = [(C0 − C)/C0] × 100%, whereas C0 is the original concentration,
and C was is concentrations at a provided time (t).
Y. Li, B. Yang and B. Liu
2.5. Photocatalytic hydrogen evolution reaction
The H2 production performances of the as-prepared TiO2/Au/Fe2O3
materials were performed under visible light illumination using a
200 W Xenon lamp (380–900 nm), and glycerol was used as a sacrificial
agent. In a typical process, 5 mg of Au loaded TiO2/Fe2O3 and unloaded
TiO2/Fe2O3 materials were dispersed into 50 mL of the water-glycerol
mixture (95/5 by v/v). The mixture was stirred under dark for 20 min.
Then the mixture was underwent N2 purging for 15 min to eliminate
the dissolved oxygen (DO). Then, the mixture was illuminated under
visible light withg constant stirring at 2500 rpm. At particular time in-
tervals, the generated H2 gas was collected through the syringe and an-
alyzed by gas chromatography using a thermal conductivity detector
(TCD) detectors using N2 carrier gas.
3. Results and discussion
3.1. `XRD analysis
In the XRD patterns from Fig. 1 of MOF derived Fe2O3/TiO2, all the
diffraction peaks marked with (a)can be indexed to Fe2O3 marked
with (a) which matched well with JCPDS card No. 33-0664 [28], with
a space group: R3c, ao = 5.03 Å bo = 5.03 Å co = 13.7 Å and TiO2
marked with (b) matched well with JCPDS card No. 65-5714 [29],
with a space group of I41/amd, ao = 3.78A bo = 3.78 Å co = 9.51 Å.
The XRD results confirmed that the Ti–Fe MOF has been successfully
converted into Fe2O3/TiO2 metal oxides. No impurity peaks or second-
ary phases are noticed, representing the high purity of Fe2O3/TiO2 nano-
composite. For Au-Fe2O3/TiO2 (4 wt%) sample, the peaks belonging to
Au (111) and (200) diffraction were observed at 2 theta value of 38.2°
and 43.8°, indicating the co-existence of Au nanoparticles [30]. Further-
more, for the Au-Fe2O3/TiO2 (4 wt%) composite the lattice parameters
was almost same as Fe2O3/TiO2 demonstrating that the crystalinity of
Fe2O3/TiO2 does not changed after the successful Au-deposition. It can
be attributed to that Au is dispersed uniformly on the Fe2O3/TiO2surface
which is highly beneficial for advanced photocatalytic performances
[31].
Fig. 1. XRD patterns of Fe2O3/TiO2 nanocomposite and 4 wt% Au-Fe2O3/TiO2
nanocomposite.
3
Journal of Molecular Liquids 322 (2021) 114815
3.2. FESEM analysis
FESEM was conducted to examine the morphological and micro-
structure of the synthesized Au-Fe2O3/TiO2 (4 wt%) sample. Fig. 2
(a–d) implies the FESEM images of Fe2O3/TiO2 samples. The Fe2O3/
TiO2 composites comprising of irregular TiO2 and cubical Fe2O3 parti-
cles exhibit fewer agglomerations.The TiO2 particles are aggregated on
the cubical Fe2O3 with an absolute size of 50–60 nm. The 4 wt% Au-
Fe2O3/ TiO2 sample was relatively smooth in the image (Fig. 2 c, d),
and the metallic Au particles were clearly distinguished in FESEM im-
ages [32].
3.3. TEM images and HRTEM analysis
As shown in Fig. 3 (a) TEM images, TiO2 has clearly exhibited particle
morphology. The 0.23 nm interplanar spacing is in accordance with that
of (110) plane of Rutile TiO2, revealing the porous structured TiO2 was
synthesized. For the Au-Fe2O3/TiO2 (4 wt%) ternary heterojunction
photocatalyst, the irregular Fe2O3 cubical particles are formed in
the range of 400–650 nm and are fewer aggregated [33]. Moreover, the
TiO2 is located around Fe2O3 particles, as illustrated in Fig. 3 (b–c). The
more detailed interface structure of Fe2O3 and TiO2 in the TEM studies re-
veals that the cubical Fe2O3 are intimately attached to the surface of TiO2
particles. The distance of lattice fringes of 0.27 nm, this is corresponding
to (104) Fe2O3 lattice plane. The HRTEM photos in Fig. 3 (d–f) exemplifies
the lattice spacing of 0.23 nm at the atomic Au sites corresponds to (111)
facets of Au, indicating the presence of Au in the ternary (4 wt%) Au-
Fe2O3/TiO2 composite. The results are matched well with the XRD analy-
sis [34]. The HRTEM results further confirmed the (4 wt%) Au-Fe2O3/TiO2
composite have successfully formed, which is highly favourable for the
separation of charge carriers in the photocatalytic pathway. Moreover,
the EDS elemental mapping of 4 wt% Au-Fe2O3/TiO2 composite further
confirms that 4 wt% Au-Fe2O3/TiO2 composite was comprised of ele-
ments Ti, O, Au and Fe, as shown in Fig. 4. It is evident that the uniform
distribution of active sites playing a significant role in accelerating the
photocatalyst process [35]. For accurate analysis the the even distribution
of Au, Fe, Ti, and O elements was recorded on the surface of (4 wt%) Au-
Fe2O3/TiO2 composite. It can be seen that Fe2O3, Au, and TiO2 particles
have been uniformly deposited, which may improve the photocatalytic
performances to a great extent [36]. Besides, the metallic Au nanoparti-
cles were deposited successfully in the areas that have higher Fe2O3 and
TiO2 concentrations. It confirms the connection between TiO2 and Fe2O3
was possible by Au nanoparticles in the ternary system [37].
3.4. XPS studies
XPS studies was performed to confirm the chemical composition
and various oxidation nature of (4 wt%) Au-Fe2O3/TiO2 composite
[38]. The XPS survey spectrum results are shown in Fig. 5a. In which,
Ti 2p, Fe 2p, O 1 s, C 1 s, and Au 4f elements were observed. The
deconvoluted Ti 2p XPS spectrum was shown in Fig. 5b. The main
peaks originated at 458.7 eV and 464.5 eV can be accredited to Ti 2p3/2
and Ti 2p1/2 binding energies, respectively. The prominent peaks ob-
served at 711.2 eV and 725.1 eV (Fig. 5c) correspond to the binding en-
ergies of Fe 2p3/2 and Fe 2p1/2 from Fe (Ⅲ), indicating the presence of
Fe2O3 [38]. Furthermore, in Fig. 5d two major peaks of Au 4f (7/2 and
5/2 spins) has been observed with binding energies of 83.5 eV and
87.4 eV, respectively, representing the continuation of metallic Au in
the ternary system [40]. The high-resolution XPS analysis of O 1s is pro-
vided in Fig. 5e and the apparent peaks observed at 529.9 eV and
531.5eV are formed from the lattice oxygen and the chemisorbed oxy-
gen of surface hydroxyls, respectively [39]. The XPS results exemplify
that the 4 wt% Au-Fe2O3/TiO2 composite have been successfully synthe-
sized using the MOF route.
Y. Li, B. Yang and B. Liu Journal of Molecular Liquids 322 (2021) 114815

Fig. 2. FESEM images of (a) Fe2O3/TiO2 nanocomposite (b-d) 4 wt% Au-Fe2O3/TiO2 nanocomposite.

Fig. 3. TEM images of (a) TiO2 (b-c) Fe2O3/TiO2 nanocomposite and HRTEM images of (d-f) 4 wt% Au-Fe2O3/TiO2 nanocomposite.

4
Y. Li, B. Yang and B. Liu Journal of Molecular Liquids 322 (2021) 114815

Fig. 4. EDS and the mapping images of 4 wt% Au-Fe2O3/TiO2 nanocomposite.

3.5. UV-DRS analysis observed that the strong absorption edge of Fe2O3/TiO2 was found
nearly at 690 nm, which confirmed that, the synthesized Fe2O3/TiO2
The optical responses of the prepared photocatalysts were evaluated which can be activated under the visible-light region. Besides, compar-
by UV-vis DRS analysis, and the spectra were given in Fig. 6a. It can be ing with the Fe2O3/TiO2, the absorption edge of the 4 wt% Au-Fe2O3/TiO2

Fig. 5. XPS spectra of 4 wt% Au-Fe2O3/TiO2 nanocomposite: (a) survey scan, (b) high resolution Ti 2p, (c) high resolution Fe 2p, (d) high resolution Au 4f, (e) high resolution O1s.

5
Y. Li, B. Yang and B. Liu
Fig. 6. (a) The UV-vis DRS and (b) Tauc plots of Fe2O3/TiO2 and 4 wt% Au-Fe2O3/TiO2 nanocomposite.
composite shows an obvious red shift further in visible range [41]. This
indicates that 4 wt% Au-Fe2O3/TiO2 composite can utilize the visible
light effectively. Furthermore, the energy gap of the Fe2O3/TiO2 and 4
wt% Au-Fe2O3/TiO2 composite estimated using the Kubelka-Munk rela-
tions as stated as follows (αhν)1/2 = A(hν -Eg), herein, α, ν, h, A and Eg
represent the coefficient of absorption, frequency, Plank constant, pro-
portionality constant and bandgap of the prepared semiconductor
[28,29]. Based on the above-mentioned calculations the bandgaps of
Fe2O3/TiO2, and 4 wt% Au-Fe2O3/TiO2 composite were estimated as
1.75 eV and 1.55 eV, and it was provided in Fig. 6b which are consistent
with the previous reports. Based on the above-mentioned calculations
the bandgaps of Fe2O3/TiO2, and 4 wt% Au-Fe2O3/TiO2 composite were
estimated as 1.75 eV and 1.55 eV, and it was provided in Fig. 6b which
are consistent with the previous reports [42].
3.6. Photocatalytic performances of prepared samples
The photocatalytic degradation properties of the as-synthesized Au-
Fe2O3/TiO2 with different weight percentages of metallic Au, Fe2O3/TiO2,
and pure TiO2 are conducted by monitoring the degradation of phenolic
compounds 2, 4-DCP, and 4-BP degraded under simulated visible light
illumination as show in Fig. 7 (a, b) [43]. The photocatalytic responses
of the Au- Fe2O3/TiO2 photocatalysts are studied towards the removal
Fig. 7. Photocatalytic degradation of 2, 4-DCP (a) and 4-BP (b) over as-prepared catalysts.
6
Journal of Molecular Liquids 322 (2021) 114815
of 2, 4-DCP, and 4-BP with the help of visible light for 90 min and 60 min.
It is further noticed that the removal of 2, 4-DCP, and 4-BP were greatly
improved with the extension of visible light access time for the synthe-
sized Au-Fe2O3/TiO2 photocatalysts [44]. The photocatalyst results con-
vey that the performance of the Au-Fe2O3/TiO2 (4%) nanocomposite is
higher than other photocatalysts with and without Au loadings [45]. It
indicates that the formation of effective heterojunction and proper load-
ings of Au in Au-Fe2O3/TiO2 photocatalyst is encouraging to the
electron-hole pairs separation, and ensuring in high degradation perfor-
mances. During the photocatalytic process, the major absorption peaks
of both 2, 4-DCP, and 4-BP have been diminished with the 90 min
and 60 min, respectively. Only 4 and 5 wt% Au- Fe2O3/TiO2 photo-
catalyst can degrade most of the 2,4-DCP, and 4-BP molecules under
visible light [46]. The photocatalytic activities improvements has been
observed and arranged in the sequence of Au- Fe2O3/TiO2 (4%) > Au-
Fe2O3/TiO2 (5%) > Au- Fe2O3/TiO2 (3%) > Au- Fe2O3/TiO2 (2%) and Au-
Fe2O3/TiO2 (0.5%) > Fe2O3/TiO2. The degradation efficiency of 2,
4-DCP, and 4-BP can be illustrated in Fig. 7a, b. The pure Fe2O3 exhibits
lower photocatalytic performances (~20.5% in 90 min for 2, 4-DCP, and
~22.5% in 60 min for 4-BP).
In contrast, the Au loaded nanorods Fe2O3/TiO2 photocatalyst exhib-
ited improved degradation performances than the bare Fe2O3 and TiO2.
For 2, 4-DCP, and 4-BP degradation, the 2 0.5% Au-doped Fe2O3/TiO2
Y. Li, B. Yang and B. Liu Journal of Molecular Liquids 322 (2021) 114815

photocatalyst and 2% Au-doped Fe2O3/TiO2 photocatalyst exhibited

similar degradation rate due to the fewer amount of Au doping in the
host Fe2O3/TiO2 [47,48]. The highest removal rate could be observed in
4 wt% Au- Fe2O3/TiO2 (94% in 90 min for 2, 4 DCP, and 97% in 60 min
for 4 BP), which is higher than 5 wt% Au- Fe2O3/TiO2 [49]. This might
be attributed to the metallic Au nanoparticles can be aggregated beyond
4% loadings. Fig. 8 (a, b) shows the kinetics, i.e. -ln(C/C0) vs. time (t) for
the all photocatalysts. The photocatalytic removal of 2, 4 DCP, and 4 BP
was considered as a Langmuir-Hinshelwood model, as pseudo first-
order reaction established by the linear connection in the images. The
4 wt% Au- Fe2O3/TiO2 nanocomposite exhibited higher rate constants
than pure Fe2O3 and TiO2 respectively (0.0076 min−1 for 2, 4-DCP,
and 0.0071 min−1) respectively. Among various ternary Au doped
Fe2O3/TiO2 nanostructures, 4 wt% Au- Fe2O3/TiO2 nanocomposite exhib-
ited the highest rate constants values than that of the pure Fe2O3 and
TiO2 alone [50]. The stability of photocatalyst is important parameter
for commercial applications. As shown in Fig. 9 after four cycles, no ob-
vious change in the 2, 4-DCP, and 4-BP photodegradation was observed,
implying the high stability of 4 wt% Au- Fe2O3/TiO2 nanocomposite Fig. 9. Recyclability of 4 wt% Au-Fe2O3/TiO2 nanocomposite for degradation of 2, 4-DCP
photocatalyst. Besides, as provided in Fig. S1 there was no difference and 4-BP under visible light.
that could be displayed in the XRD patterns of 4 wt% Au- Fe2O3/
TiO2 nanocomposite after cycle experiments indicating that the crystal
phases of the prepared sample did not change. This result further con- have proven that there is no H2 generation has been observed without
firmed the high stability of the 4 wt% Au- Fe2O3/TiO2 nanocomposite to- the aid of any photocatalyst, and visible light irradiation exemplifies
wards phenolic compounds degradations [51]. that no H2 gas is produced by simply in photolysis process [53]. It can
The radicals trapping studies were recorded in revealing the main be seen that pure Fe2O3 has insufficient H2 production. Even though
reactive species generated in the photocatalytic pathway as shown in Fe2O3 shows an excellent visible light absorption (i.e., low bandgap),
Fig. 10 (a, b). In the tests, isopropanol alcohol (IPA), Benzoquinone but the H2 production activity was not appreciable owing to its quick re-
(BQ), and silver nitrate (AgNO3) were used as radical scavengers for hy- combination reactions of electron-hole pairs, in the medium and
droxyl radicals (.OH), superoxide anion radicals (.O− 2 ), and photo- 58 μmol g−1 h−1of H2 was generated from pure Fe2O3, which is compar-
generated electron (e−) respectively. The degradation efficiency of 4 atively lower for commercialization. Similarly, pure TiO2 made a
wt% Au- Fe2O3/TiO2 nanocompositefor degrading 2, 4-DCP, and 4-BP 142 μmol g−1 h−1 of H2, and it was studied that the H2 generation of
without the addition of IPA, BQ, and AgNO3 under visible light illumina- pure TiO2 is constrained by slow kinetic reactions for water splitting
tion within 90 and 60 min was used for comparison, as provided in due to the poor redox-active sites in TiO2. After the coupling of Fe2O3
Fig. The degradation performances were slightly decreased by introduc- with TiO2, the H2 generation was reached to about 392 μmol g−1 h−1,
ing AgNO3, however, the degradation was inhibited significantly in IPA, and this is almost twice than the pure Fe2O3. A sudden jump in the H2
BQ revealing the •OH and •O− 2 play a significant role in both 2, 4 DCP, and production rate was observed when Au was introduced as 4 wt% Au-
4 BP degradation processes [52]. Fe2O3/TiO2 nanocomposite it reached about 590 μmol g−1 h−1. This
could be ascribed to the existence of small amounts of Au on the
3.7. Hydrogen production reactions Fe2O3/TiO2 surface, which alters and slow down the recombination
rate, which arises from the proper bandgap alignment of these two
The H2 production performances of the synthesized Au-Fe2O3/TiO2 Fe2O3 and TiO2 semiconductors by proper Au loading [54]. It is observed
photocatalyst were investigated from water-splitting using glycerol as that the appropriate interactions between the coupled photocatalyst
a sacrificial reagent under the visible light Fig. 11 (a). Blank studies play a pivotal role in H2 production. Furthermore, a promising

Fig. 8. Corresponding kinetics plots towards the degradation of 2, 4-DCP (a) and 4-BP (b) over as-prepared photocatalysts under visible light.

7
Y. Li, B. Yang and B. Liu
Fig. 10. Active species trapping experiments of 4 wt% Au-Fe2O3/TiO2 nanocomposite in degrading 2, 4-DCP (a) and 4-BP (b) under visible light.
photocatalyst may be a great strength for commercial applications.
Therefore, the photocatalytic stability of 4 wt% Au- Fe2O3/TiO2 nanocom-
posite was recorded with the continuation of the H2 production reaction
for 7 h. As illustrated in Fig. 11 (b). a fewer decline in H2 production was
observed after repeat the experiments three times The H2 generation
results affirm that the 4 wt% Au- Fe2O3/TiO2 nanocomposite has prone to
stable for H2 production, which may be ascribed to the effectual electron
transport kinetics between the Fe2O3/TiO2 interface by Au deposition
and stability of host TiO2 for H2 production using the photocatalyst
process [55].
3.8. Photocatalytic performance mechanism
Based on the above degradation reactions and H2 production results,
plausible photocatalytic mechanisms for the Au- Fe2O3/TiO2 system has
been proposed [56]. Thus, it can be realized that the effective
heterojunction formedbetween the Fe2O3 and TiO2phases are responsi-
ble for the improved photocatalytic H2 production and degradation of 2,
4-DCP, and 4-B P. The Au was decorated on the Fe2O3/TiO2surface, H2
Fig. 11. (a) Photocatalytic hydrogen generation activities (b) stability of 4 wt% Au-Fe2O3/TiO2 nanocomposite.
8
Journal of Molecular Liquids 322 (2021) 114815
generation and 2,4 -DCP and 4 -BP removals were extended to a great
extent. The improvement of photocatalytic performance might be
attributed due to the SPR effectsby Au nanoparticles. In general, Au dec-
orated on the surface of the Fe2O3/TiO2 converts the photon energy from
visible light into plasmonic energy, and then injects it to the Fe2O3/TiO2,
by this meansenhancing the light-harvesting capability and the photo-
catalytic performances [57]. It is recognized that the positions in the
VB and CB potentials of a Fe2O3/TiO2 play a significant role in photocat-
alytic performances. The photocatalytic mechanisms of the Fe2O3/TiO2
system is mainly due to the as usual heterojunction formation and the
movement of the generated electrons transfers from the CB of TiO2
with highly negative edge potential value to the CB of Fe2O3,which has
more positive potential [58]. Therefore, in this ternary photocatalyst,
Au nanoparticles with the aid of SPR effect and both Fe2O3 and TiO2
with a narrow bandgap value of the Au- Fe2O3/TiO2system can act as
photosensitizer under the visible light. The absorption of a photon by
Fe2O3 and TiO2 aids to the easy excitation of electrons from their band
levels, and exitthe holes in their VB [59]. The noble metal Au adhered
at the heterojunctions surface with low resistance value, which can
Y. Li, B. Yang and B. Liu
Fig. 12. Schematic diagram of photocatalysis over 4 wt% Au-Fe2O3/TiO2 nanocomposite under visible light.
act as an efficient e−mediator to improve the movement of electron be-
tween the Fe2O3 and TiO2 interface. Hence, the ternary Au- Fe2O3/TiO2
nanocomposites improve the electron-hole separation, which results
in better photocatalytic performances of H2 generation and degradation
of various phenolic compounds, as shown in Fig. 12 [60–64].
4. Conclusion
In summary, the Au- Fe2O3/TiO2 nanocomposite photocatalysts
were fabricated via a MOF assisted solvothermal reaction. HRTEM im-
ages suggested that an intimate interface between Fe2O3 and TiO2and
Au nanoparticles formed in the effectiveheterojunctions systems.
FESEM and EDS results had collectively validated the enhanced charge
transfer within Au- Fe2O3/TiO2 nanocomposite. The photocatalytic per-
formance of ternary composite Au-Fe2O3/TiO2 photocatalysts was stud-
ied by the removal of 2, 4-DCP, and 4-BP degradation under visiblelight.
Especially, the removal 2,4 DCPremoval was up to 95% over the Au-
Fe2O3/TiO2 nanocomposite after irradiation for 90 min and 4 BP exhib-
ited 97% removal within 60 min. The high photocatalytic degradation
efficiency of Au-Fe2O3/TiO2 nanocomposite was mainly credited to the
lavish reactive sites and enhanced the separation efficiencies of
photogenerated carriers by Au deposition. It was noted that Au was
acted asan efficient redox mediator of the heterostructure between
Fe2O3 and TiO2to promote the electron transfer. The highest H2 produc-
tion of 590 μmol g−1 h−1, witha quantum yield of 12%, was obtained
using theglycerol as sacrificial reagent using 4 wt% Au- Fe2O3/TiO2 nano-
composite. Consequently, this study indicated that Au-Fe2O3/TiO2
photocatalyst employing noble metal nanoparticles was a gifted
photocatalyst material for waste-water treatment and hydrogen pro-
duction in the future.
Declaration of Competing Interest
None.
Acknowledgements
This work was financially supported by the Application and Funda-
mental Research Project of Shanxi Province (201801D121270,
201801D121236) and National Natural Science Foundation of China
(No. 21571117, 21575083).
9
Journal of Molecular Liquids 322 (2021) 114815
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.molliq.2020.114815.
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