Chemical Engineering Journal 402 (2020) 126193

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Chemical Engineering Journal

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

Z‑scheme SnFe2O4/α-Fe2O3 micro-octahedron with intimated interface for T

photocatalytic CO2 reduction
⁎
Yuefa Jiaa,b,c, Weibin Zhangd, Jeong Yeon Doe, Misook Kange, Chunli Liuc,
a
Chemical Engineering and Technology, School of Water and Environment, Chang'an University, Xi'an 710054, PR China
b
Key Laboratory of Subsurface Hydrology and Ecological Effects in Arid Region (Chang'an University), Xi'an 710054, PR China
c
Department of Physics and Oxide Research Center, Hankuk University of Foreign Studies, Yongin 17035, Republic of Korea
d
School of Physics and Optoelectronic Engineering, Yangtze University, Jingzhou 434023, PR China
e
Department of Chemistry, College of Science, Yeungnam University, Gyeongsan 38541, Gyeongbuk, Republic of Korea

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• FeTheO micro-octahedrons SnFe O /α-2

heterostructure was fabricated
4

2 3
by an in-situ reaction.
• The heterostructure significantly en-
hanced the photoreduction of CO . 2

• The intimate contact was found be-

tween SnFe O and α-Fe O .
2 4 2 3

• Z-scheme charge transfer and close

contact interface are supposed to ex-
plain the excellent performance of the
heterojunction.

A R T I C LE I N FO A B S T R A C T

Keywords: Interface engineering is a very important issue in achieving high efficiency in heterojunction photocatalysts.
SnFe2O4 Herein, we report an originally designed heterojunction photocatalyst with seamless contact. Its novelty includes
CO2 reduction the following two respects: (1) two Fe-based oxides, i.e., SnFe2O4 and hematite Fe2O3 (α-Fe2O3), with suitable
Seamless contact band structures were selected to promote charge separation, and (2) a seamless contact was achieved at the
Micro-octahedrons
interface taking advantage of the commonly shared Fe element, i.e., converting partial of the Fe ions on the
Z-scheme
surface of micro-octahedrons SnFe2O4 nanocrystals into α-Fe2O3 through thermal treatment (Octa-SnFe2O4/α-
Fe2O3). Characterization results confirmed the formation of seamless contact with large area at the interface, and
the significantly enhanced Z-scheme charge separation efficiency. The seamless Octa-SnFe2O4/α-Fe2O3 het-
erojunction could deliver a higher CO2 photocatalytic reduction activity with production rates of 2.87 μmol/g/h
for CO and 0.64 μmol/g/h for CH4, which is 13.7 times and 6.4 times higher than Octa-SnFe2O4, and 2.3 times
and 5.3 times than those of conventionally prepared SnFe2O4/α-Fe2O3 composite counterparts. This work in-
dicated that the ferrite-based close-contacted heterojunctions can be further investigated as promising photo-
catalysts in the environmental and energy applications.

1. Introduction unlimited solar energy to produce hydrocarbon fuels has been con-
sidered as one of the most promising solution for overcoming the global
Semiconductor photocatalytic reduction of CO2 utilizing the energy crisis and serious environmental pollution [1,2]. Since the first

⁎
Corresponding author.
E-mail address: chunliliu@hufs.ac.kr (C. Liu).

https://doi.org/10.1016/j.cej.2020.126193
Received 1 June 2020; Received in revised form 25 June 2020; Accepted 5 July 2020
Available online 11 July 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
Y. Jia, et al.
report of using TiO2 as a photocatalyst, many semiconductor materials
have been investigated as applicable candidates for CO2 photocatalytic
reduction [3]. Nevertheless, it is well known that single materials suffer
from limited light absorption and fast recombination of the photo-
generated electron-hole pairs, which lead to an unsatisfactory photo-
catalytic efficiency [4]. Well-designed composite photocatalysts can
effectively overcome the above-mentioned issues, and various compo-
site photocatalysts have been reported for improved CO2 reduction ef-
ficiency [5,6].
To maximize the performance of the composite photocatalysts, the
component materials should be carefully selected to realize not only
wide-band solar light absorption but also effective charge transfer and
separation at the heterojunction interface. Firstly, the component ma-
terials should possess suitable energy bandgap energy and band edge
positions, so that wide band light absorption and a Z-scheme charge
transfer can be achieved [7]. Secondly, closed contact is highly desir-
able at the interface of the heterojunction to efficiently promote the
migration and separation of the electron-hole pairs [8]. Besides com-
posites that consist quite different materials, heterojunctions that are
made from materials with comment elements have recently emerged as
an effective approach to achieve close contact at the interface. For ex-
ample, SnS2/SnO2, Cs2SnI6/SnS2, Zn2SnO4/SnO2, and Li2TiO3/TiO2
with close contacts have been reported as effective visible light re-
sponse photocatalysts for boosting photocatalytic CO2 reduction
[9–12]. Obviously, sharing a common metal element by the two ma-
terials in the hybrid heterogeneous complex can effectively prolong the
charge carrier lifetime and increase the carrier density [13].
Spinel tin ferrite (SnFe2O4) has recently been frequently reported in
various photocatalytic systems [14]. SnFe2O4 has a band gap energy of
1.9 eV with a conduction band edge potential of −1.45 V vs NHE,
therefore SnFe2O4 is suitable for visible light absorption and its con-
duction band electrons possess strong reduction ability [15]. In addi-
tion, the room temperature magnetization of SnFe2O4 can enable easy
magnetic separation and recycle of the used photocatalyst. As a com-
ponent material, SnFe2O4 has been used in various composite photo-
catalysts to utilize the above advantages, such as SnFe2O4-graphitic
carbon nitride, sulfur-doped SnFe2O4/graphene and SnFe2O4/SnO2/
PANI composites [16–18]. On the other hand, due to the difficulty in
controlling the crystallinity and morphology, satisfactory close con-
tacted interface between SnFe2O4 and the partner materials remains a
challenge, which inhibits the further improvement of the activity of the
SnFe2O4-based composite photocatalysts.
In this work we select α-Fe2O3 to couple with SnFe2O4 to form the
seamless heterojunction for CO2 reduction. α-Fe2O3 is a narrow
bandgap (Eg = 1.68 or 1.69 eV) semiconductor that has also been ex-
plored as a photocatalyst due to its low synthesis cost, high stability,
and environment-friendly feature [19,20]. α-Fe2O3 has two advantages
for coupling with SnFe2O4. Firstly, the valence band (VB) edge positions
of α-Fe2O3 is at 2.48 V, which implies a strong oxidation capability of
the VB holes [7]. Therefore, the relative band edge positions of α-Fe2O3
and SnFe2O4 are suitable for inducing the Z-scheme charge transfer at
the heterojunction interface, so that the redox activity of the electrons
and holes can both be preserved. Secondly, since SnFe2O4 and α-Fe2O3
share a common element Fe, it is possible to form ‘zero distance’ het-
erojunction as demonstrated by several recent reports [9–12]. Although
there are quite a few composite photocatalysts with similar components
reported in the literature, most of these composites were fabricated by
physical mixing or stepwise solvothermal methods, wherein the het-
erojunctions are mainly formed randomly in the composite with irre-
gular morphology [7,16–18]. In this case, a high resistive interface can
be expected, which can significantly limit the separation of the pho-
togenerated charge carries and thus the photocatalytic performance.
Herein we report for the first time a seamless contact micro-octa-
hedrons SnFe2O4/α-Fe2O3 (Octa-SnFe2O4/α-Fe2O3) heterojunction
with high photocatalytic CO2 reduction efficiency. The seamless close
contact was made possible by preparing SnFe2O4 nanoparticles with
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Chemical Engineering Journal 402 (2020) 126193
well-defined octahedral morphology as the starting material instead of
irregular nanoparticles, then converting partial of the Octa-SnFe2O4
surface into α-Fe2O3 through thermal treatment. Through our ap-
proach, we were able to achieve not only close contact at the Octa-
SnFe2O4/α-Fe2O3 interface, but also large area surface contact instead
of point contact. The structural, optical, and electrochemical char-
acterization confirmed the effective separation of photo-generated
electrons and holes through a Z-scheme charge transfer at the Octa-
SnFe2O4/α-Fe2O3 interface, which led to a much improved photo-
catalytic CO2 reduction activity.
2. Experimental section
All reagents in this work were of analytical purity and were used
without further purification. In a typical synthesis, 0.322 g of SnCl2 and
0.656 g of FeCl2·4H2O were first dissolved in 50 mL ethylene glycol to
form a transparent solution. Then 10 mL NaOH solution (50 wt%
NaOH) was added to the above solution, and the mixture was stirred
vigorously for several hours before being transferred to a Teflon-lined
stainless-steel autoclave (100 mL capacity). The autoclave was placed
in a furnace held at 200 °C for 15 h. After the autoclave was cooled
down to room temperature naturally, the resulting precipitate was
centrifuged, washed with anhydrous ethanol for several times, and fi-
nally dried in oven at 80 °C for 12 h. The precipitate was then calcined
at 250, 300 and 350 °C for 3 h to obtain Octa-SnFe2O4/α-Fe2O3 with
different compositions, respectively. According to their X-ray diffrac-
tion (XRD) results, the content of α-Fe2O3 in Octa-SnFe2O4/α-Fe2O3
were determined to be 8.13 wt%, 12.45 wt%, and 16.52 wt%, respec-
tively. The α-Fe2O3 nanoparticles were purchased from Sigma-Aldrich
Chemicals Co. Ltd.
For comparison, the contrastive SnFe2O4/α-Fe2O3 composite was
prepared by a hydrothermal route (sample denoted as SnFe2O4/α-
Fe2O3 (H)). In detail, Octa-SnFe2O4 were dispersed into 50 mL of dis-
tilled water with sonication for 30 min. Then, Fe(NO3)3·9H2O was
added to the above solution and vigorously stirred for 1 h to obtain a
homogeneous suspension. NH4OH was added to the above solution
under continuous stirring to adjust the pH value (about 9). After being
stirred for 30 min, the solution was transferred into a 100 mL Teflon-
lined stainless-steel autoclave. The sealed tank was heated to and
maintained at 150 °C for 15 h. Finally, the SnFe2O4/α-Fe2O3 (H)
composite was obtained with 12.45 wt% α-Fe2O3. Furthermore,
SnFe2O4/α-Fe2O3 composite was also synthesized by mechanically
mixed method (sample denoted as SnFe2O4/α-Fe2O3 (M)). Briefly,
purchased α-Fe2O3 powders and Octa-SnFe2O4 were grinded for
30 min. In this manner, SnFe2O4/α-Fe2O3 (M) with 12.45 wt% α-Fe2O3
was obtained.
The detailed of characterization, photocatalytic measurement, and
electronic structure calculation are given in the Supporting
Information.
3. Results and discussion
The Octa-SnFe2O4/α-Fe2O3 were prepared through a two-step
method that included a solvothermal process followed by thermal
treatment (Scheme 1). The first step (solvothermal process) led to the
formation of the Octa-SnFe2O4. Then some of the Fe ions on the surface
of the Octa-SnFe2O4 were oxidized to α-Fe2O3 by calcination at a higher
temperature (≥250 °C). As shown in the X-ray diffraction (XRD) pat-
terns (Fig. 1), Octa-SnFe2O4 matched well with those of Fe3O4
(PDF#19–0629) and SnFe2O4 reported in the literature [8–11]. In ad-
dition, typical diffraction peaks of α-Fe2O3 were observed from Octa-
SnFe2O4/α-Fe2O3, confirming the existence of α-Fe2O3. The α-Fe2O3
content in the Octa-SnFe2O4/α-Fe2O3 composite was found to be de-
pendent on the calcination temperatures. For comparison, Octa-
SnFe2O4/α-Fe2O3 with 8.13, 12.45, and 16.52 wt% of α-Fe2O3 were
synthesized through calcination at 250, 300 and 350 °C for 3 h,
Y. Jia, et al.
Scheme 1. Illustration of the formation process of Octa-SnFe2O4/α-Fe2O3.
Fig. 1. XRD patterns of Octa-SnFe2O4/α-Fe2O3.
respectively.
The hydrothermally prepared SnFe2O4 showed well defined octa-
hedron shape, with a quite uniform size about 300 nm (Fig. S1a). The
different calcination temperature did not affect the SnFe2O4 mor-
phology (Fig. 2a and 2b, Fig. S1b and c). Especially, it is noted from the
TEM image that the surface of the micro-octahedrons composite was
quite smooth, with no protrusion or particles observed (Fig. 2c). Ele-
mental mappings of Octa-SnFe2O4/α-Fe2O3 revealed the uniform dis-
tribution of Fe, O and Sn in the composite (Fig. 2d-2f). The existence of
α-Fe2O3 has been confirmed through detailed TEM analysis. Typically,
the high-resolution TEM (HRTEM) images of the two locations labelled
as 1 and 2 in Fig. 2g are shown in Fig. 2h-2i and Fig. 2j-2 k, respec-
tively. Fig. 2h and 2i showed that a thin layer (~2 nm) of α-Fe2O3 were
formed at some parts of the Octa-SnFe2O4 surface. Distinct lattice
spacings of 0.486 nm and 0.250 nm were clearly observed, which can
be indexed to the SnFe2O4 (1 1 1) plane and the α-Fe2O3 (1 1 0) plane,
respectively. The fast Fourier transform (FFT) of the corresponding area
also showed consistent result (inset of Fig. 2h). In Fig. 2j, an obvious
large area of α-Fe2O3 nanocrystalline was grown on the surface of the
Octa-SnFe2O4. In this region, different lattice spacings of 0.245 and
0.265 nm were observed, which corresponds to the (2 2 2) plane of
SnFe2O4 and (1 0 4) plane of α-Fe2O3, respectively (Fig. 2k). The SEM
and TEM analysis revealed that nanocrystalline α-Fe2O3 covered part of
the Octa-SnFe2O4 surface with large contacting interface, and there was
no other interfacial layer between α-Fe2O3 and Octa-SnFe2O4. There-
fore, improved charge migration across the seamless heterojunction
interface can be expected as compared with other composites with
normally observed point contact between surface decorated nano-
particles and the host materials [16–18].
XPS was further employed to investigate the surface chemical
composition and chemical states of purchased α-Fe2O3, Octa-SnFe2O4
and Octa-SnFe2O4/α-Fe2O3, wherein Fe2p, Sn3d and O1s were detected
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Chemical Engineering Journal 402 (2020) 126193
(Fig. 3a). In the high-resolution Fe2p spectrum (Fig. 3b), the binding
energies at 710.1 eV, 712.2 eV, and 724.1 eV were from Fe 2p3/2 and Fe
2p1/2, respectively, suggesting Fe3+ mainly existed on the surface [21].
Besides, the shakeup satellite peak at 717.eV was the characteristic of
Fe3+ in purchased α-Fe2O3, Octa-SnFe2O4 and Octa-SnFe2O4/α-
Fe2O3[22]. The Sn 3d spectrum of the Octa-SnFe2O4 and Octa-SnFe2O4/
α-Fe2O3 were shown in Fig. 3c. The two peaks at 485.8 eV and 494.4 eV
in the XPS spectrum of Sn can be assigned to Sn2+ [16]. The other two
peaks at 486.2 eV and 496.0 eV are from the lattice Sn (Sn4+ oxidation
state) [23]. Therefore, the XPS results confirm that both Sn2+ and Sn4+
ions exist in Octa-SnFe2O4 and Octa-SnFe2O4/α-Fe2O3. As shown in
Fig. 3d, the O 1s spectrum could be fitted to three peaks at 529.6 eV,
531.2 eV and 532.0 eV. The first two peaks can be attributed to lattice
oxygen and oxygen vacancies [24]. The later at 532.0 eV may belong to
the adsorbed H2O [25]. The peak area percentage attributed to oxygen
vacancies is smaller in Octa-SnFe2O4/α-Fe2O3 than Octa-SnFe2O4, in-
dicating that the Octa-SnFe2O4/α-Fe2O3 possess less oxygen vacancies
and hydroxyl species. The calcination process performed in air could
lead to the filling of some oxygen vacancies on the surface of Octa-
SnFe2O4/α-Fe2O3 [26].
The content of α-Fe2O3 in the composite has been found to affect the
photocatalytic CO2 reduction efficiency, as shown in Fig. 4a. The main
products of the CO2 photocatalytic reduction were CO and CH4. No
noticeable CO and CH4 were produced for purchased α-Fe2O3, and
Octa-SnFe2O4 showed the average CO and CH4 production rate of
0.21 μmol/g/h and 0.10 μmol/g/h, respectively. Notably, the in-
corporation of α-Fe2O3 significantly boosted the catalytic activity of
Octa-SnFe2O4, and Octa-SnFe2O4/α-Fe2O3 with 12.45 wt% of α-Fe2O3
showed the best performance, reaching 2.87 μmol/g/h for CO and
0.64 μmol/g/h for CH4, which were about 13.7 and 6.4 times higher
than that of Octa-SnFe2O4. Higher content of α-Fe2O3 deteriorated the
photocatalytic CO2 reduction performance, which can be ascribed to
the excessive α-Fe2O3 acting as the recombination center for the elec-
trons and holes [27]. The discussion hereafter will be focused on Octa-
SnFe2O4/α-Fe2O3 with 12.45 wt% of α-Fe2O3. The Octa-SnFe2O4/α-
Fe2O3 showed stable performance in recycled usage with magnetic re-
collection. Only ~ 10% deactivation was observed after three con-
secutive cycles, as shown in Fig. 4b. Furthermore, there were almost no
change in phase (Fig. 4a), morphology (Fig. 4b and Fig. S2a), and
surface chemical composition and chemical states (Fig. S2b–e) observed
in the recycled samples, certifying its favorable photostability.
Various characterizations revealed that the coupling of α-Fe2O3
with Octa-SnFe2O4 can effectively improve the surface activity and the
separation efficiency of the photogenerated charge carriers, which re-
sulted in the enhanced CO2 reduction performance. Fig. 5a shows that
the composite has superior CO2 adsorption ability as compared with
either α-Fe2O3 or Octa-SnFe2O4. At P/P0 = 1.0, the CO2 adsorption
ability of α-Fe2O3, Octa-SnFe2O4, and Octa-SnFe2O4/α-Fe2O3 is 0.34,
0.57, and 0.83 cm3/g, respectively. Therefore, the better CO2 adsorp-
tion can directly lead to higher CO2 reduction performance [28]. Fur-
thermore, the temperature programmed desorption (TPD) measure-
ments of CO and CH4 indicated that these reduction products were
more easily desorbed from the Octa-SnFe2O4/α-Fe2O3 composite
Y. Jia, et al.
Fig. 2. FESEM (a, b) and TEM (c) images of Octa-SnFe2O4/α-Fe2O3, and its corresponding elemental mapping images (d–f), HRTEM image of Octa-SnFe2O4/α-Fe2O3
(g) and corresponding enlarged HRTEM images of point 1 (h, i) and point 2 (j, k). The corresponding FFT pattern is shown in the inset of (h).
surface. As shown in Fig. 5b and 5c, weak (100–200 °C), medium
(300–450 °C) and strong (500–800 °C) basic sites were observed from
Octa-SnFe2O4, implying that the strong CO and CH4 adsorption ability
of Octa-SnFe2O4. On the contrary, after the introduction of α-Fe2O3, no
CO desorption peak and only CH4 desorption peaks can be identified in
less than 450 °C from the composite. This result suggests that the gas
products desorb more easily from the surface of Octa-SnFe2O4/α-Fe2O3,
which should be helpful in sustaining the active sites and the CO2 re-
duction reaction at the surface [29].
Moreover, the CO2 adsorption energies on α-Fe2O3, SnFe2O4, and
SnFe2O4/α-Fe2O3 surface were calculated. As shown in Fig. 5d, pure
SnFe2O4 exhibits a stronger CO2 (−0.478 eV) affinity than α-Fe2O3
(0.018 eV). Because the conduction band potential of SnFe2O4
(−1.27 V vs NHE) is more negative than CO/CO2 (−0.53 V vs NHE)
and CH4/CO2 (−0.24 V vs NHE), CO2 can be easily converted to CO
and CH4. Moreover, the adsorption energy of CO2 on the SnFe2O4/α-
Fe2O3 surface (−0.694 eV) is higher than the others. As represented in
Fig. 5e and 5f, the adsorption energies of CO and CH4 on surface of
SnFe2O4 (−0.677 eV and −0.536 eV) are stronger than α-Fe2O3
(0.025 eV and −0.076 eV), indicating that the desorption of CO and
CH4 from α-Fe2O3 are easier than that on SnFe2O4. Moreover, the ad-
sorption energies of CO and CH4 on the SnFe2O4/α-Fe2O3 surface show
remarkable decrease, indicating that introducing α-Fe2O3 into SnFe2O4
4
Chemical Engineering Journal 402 (2020) 126193
is benefit for CO and CH4 liberation from the catalyst. Therefore, the-
oretical calculations demonstrated that Octa-SnFe2O4/α-Fe2O3 pos-
sessed improved CO2 adsorption activity and better CO and CH4 lib-
eration ability, being consistent with the experimental characterization
results.
To determine the charge flow and the energy level of the Octa-
SnFe2O4/α-Fe2O3 heterojunction, UPS measurement was performed
(Fig. 6a). The upper onset and secondary onset in the UPS spectra for
SnFe2O4 were found as 17.00 and 5.00 eV, respectively. The work
function (φ) of SnFe2O4 is 4.72 eV vs vacuum as obtained by formula
1[30]:
φ = 21.22 − Δ E− 4.5 (1)
where ΔE is the energy distance from the upper onset to secondary
onset (Fig. 6a), the excitation energy of He I UPS spectra is 21.22 eV,
the work function of the detector is 4.5 eV. Therefore, the Fermi level
(Ef) of SnFe2O4 is −4.72 eV vs vacuum. As shown in Fig. 6b, the XPS
valence band spectrum shows that the valence band level (EVB) of
SnFe2O4 is 0.45 eV versus vacuum level below Ef. As a result, the EVB of
SnFe2O4 is −5.17 eV vs vacuum. The band gap energy (Eg) value is
2.00 eV for SnFe2O4 from UV–vis diffuse reflectance spectra (Fig. 6c).
Therefore, the conduction band (ECB) of SnFe2O4 is located at −3.17 eV
vs vacuum level. Similarly, as shown in Fig. 6a-6c, Ef, EVB, Eg and ECB of
α-Fe2O3 are −5.72, −6.92, 2.25, and −4.67 eV vs vacuum level,
Y. Jia, et al.
Fig. 3. Survey XPS spectra (a), high-resolution XPS spectra of Fe 2p (b), Sn3d (c), and O 1s (d) spectra of purchased α-Fe2O3, Octa-SnFe2O4 and Octa-SnFe2O4/α-
Fe2O3.
respectively. These energy values (vs vacuum) in electronvolts are
converted into normal electrode potential (vs NHE) in volts, using the
formula 2[31]:
E vacuum (eV) = −ENHE (V) − 4.44(298K)
Therefore, the band positions of SnFe2O4 are −1.27 and 0.73 V vs
NHE, those of α-Fe2O3 were calculated at 0.23 and 2.48 V vs NHE.
Accordingly, the estimated band positions for α-Fe2O3 and SnFe2O4
matched well with the requirement for direct Z-scheme system.
Furthermore, the Z-scheme charge transfer in Octa-SnFe2O4/α-
Fe2O3 were confirmed through ESR measurement. Since the band edge
position of ECB in α-Fe2O3 (0.23 V vs NHE) is at more positive potential
than that of O2/%O2− reaction (−0.33 V vs NHE) [32], no %O2− radical
signal can be detected from α-Fe2O3, as shown in Fig. 6d. However, the
DMPO-%O2− signal from Octa-SnFe2O4/α-Fe2O3 has stronger char-
acteristic peaks than Octa-SnFe2O4 under visible light irradiation. Si-
milar observation was obtained in the DMPO-%OH spectra (Fig. 6e).
There was no DMPO-%OH signal observed from Octa-SnFe2O4 because
the potential of the EVB band edge position of SnFe2O4 (0.73 V vs NHE)
is more negative than that of OH−/%OH (1.99 V vs NHE) and H2O/%OH
(2.34 V vs NHE) reactions [7]. Contrarily, Octa-SnFe2O4/α-Fe2O3
showed DMPO-%OH signal with stronger characteristic peaks than α-
Fe2O3. The ESR measurement evidenced that the Octa-SnFe2O4/α-
Chemical Engineering Journal 402 (2020) 126193
Fe2O3 interface enabled the Z-scheme migration of charges, so that the
photo-generated electrons and holes were effectively separated in the
CB of SnFe2O4 and the VB of α-Fe2O3, respectively (Fig. 6f). As a result,
the redox capability of both component materials was preserved to
(2) improve the photocatalytic efficiency.
The efficient separation of the photo-generated electrons and holes
across the close contacted heterojunction resulted in improved optical
and photo-electrochemical properties, as confirmed from the photo-
luminescence spectra (PL), time-resolved PL spectroscopy, and photo-
electrochemical characterizations. Apparently, the emission of Octa-
SnFe2O4/α-Fe2O3 was strongly quenched compared with that of the
purchased α-Fe2O3 and Octa-SnFe2O4 (Fig. 7a). Meanwhile, time-re-
solved PL spectroscopy revealed that the average emission lifetime of
Octa-SnFe2O4 (2.98 ns) was prolonged to 5.49 ns after forming Octa-
SnFe2O4/α-Fe2O3 heterojunction (Fig. 7b). Therefore, the efficient se-
paration and migration of interfacial charge carriers were achieved in
the Octa-SnFe2O4/α-Fe2O3. Besides, Octa-SnFe2O4/α-Fe2O3 had the
highest photocurrent in the transient photocurrent spectra (Fig. 7c),
suggesting the enhanced generation and transfer of photogeneration
electron-hole pairs in the photocatalyst. Also, EIS tests (Fig. 7d) re-
vealed that Octa-SnFe2O4/α-Fe2O3 manifests the smallest semicircle in
Nyquist plots, suggesting the lowest charge transfer resistance which
facilitates the transport and separation of photoexcited electron-hole
5
Y. Jia, et al.
Fig. 4. Average CO and CH4 production rates of various Octa-SnFe2O4/α-Fe2O3 (a), recycling performance of Octa-SnFe2O4/α-Fe2O3 (b), the XRD patterns (c) and
TEM (d) for the fresh and used Octa-SnFe2O4/α-Fe2O3.
pairs [24]. To further confirm the charge transfer process, the cyclic
voltammograms curves were recorded for determining the flow direc-
tion of electron-hole in samples (Fig. 7e). The higher oxidation and
reduction potential were observed in Octa-SnFe2O4/α-Fe2O3 than that
in purchased α-Fe2O3 and Octa-SnFe2O4, implying enhanced oxidiz-
ability and reducibility of the α-Fe2O3 decorated Octa-SnFe2O4. If Octa-
SnFe2O4/α-Fe2O3 is a conventional heterojunction, the redox ability
would be declined due to the migration of excited electrons downward
and holes upward. Therefore, the formation of Z-scheme charges
transfer pathway in Octa-SnFe2O4/α-Fe2O3 is further confirmed by the
cyclic voltammograms examination. All these results illustrated that
Octa-SnFe2O4/α-Fe2O3 should be the optimal photocatalyst in separa-
tion and transfer of the photo-induced charges.
The determinant role of the close contact in the heterojunction can
be demonstrated by comparing SnFe2O4/α-Fe2O3 composites prepared
through other approaches (Fig. S3a). Fig. 8a and 8b shows the typical
SEM image of SnFe2O4/α-Fe2O3 prepared by mechanically mixing Octa-
SnFe2O4 with purchased α-Fe2O3, which is labelled as SnFe2O4/α-
Fe2O3 (M), and by hydrothermal processing of Octa-SnFe2O4 with Fe
(NO)3·9H2O, which is labelled as SnFe2O4/α-Fe2O3 (H). Obviously,
these samples exhibited separated or aggregated α-Fe2O3 particles from
Octa-SnFe2O4, showing quite different morphologies from the Octa-
SnFe2O4/α-Fe2O3. The SEM images directly evidenced the importance
and uniqueness of the procedure employed in this work to construct the
close contact between α-Fe2O3 and Octa-SnFe2O4. In addition, despite
the similar phase composition, Octa-SnFe2O4/α-Fe2O3 showed much
enhanced light absorption, especially for wavelength longer than
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Chemical Engineering Journal 402 (2020) 126193
600 nm (Fig. S3b).
The close contact showed significant effect in enhancing the elec-
trochemical properties of the composites. Charge separation behaviors
of those three heterostructures were characterized by time-resolved PL,
surface photovoltage (SPV) and electrochemical impedance spectro-
scopy (EIS). Evidently, the average lifetime of the photogenerated
charge carriers in Octa-SnFe2O4/α-Fe2O3 (5.49 ns) was strikingly more
prolonged than that of SnFe2O4/α-Fe2O3 (M) (0.68 ns) and SnFe2O4/α-
Fe2O3 (H) composites (3.41 ns) (Fig. 8c). It is well-known that a longer
lifetime of electrons and holes implies a high probability for partici-
pation in photocatalytic reaction and improved activity [33]. As shown
in Fig. 8d, no significant SPV signals were observed in the SnFe2O4/α-
Fe2O3 (M) due to the rapid charge carrier recombination. In contrast,
the most intensive SPV response was observed in Octa-SnFe2O4/α-
Fe2O3, suggesting that the as-prepared close contact heterostructure
had a relatively low recombination rate of photogenerated electrons
and holes. Therefore, it can be reasonably inferred that the in-situ
formed close contact interfaces during calcination benefited the accel-
eration of the charge transfer between α-Fe2O3 and SnFe2O4. Also, EIS
curves revealed that Octa-SnFe2O4/α-Fe2O3 manifested the smallest
semicircle in the Nyquist plots (Fig. 8e), suggesting the minimum the
charge transfer resistance at the Octa-SnFe2O4/α-Fe2O3 interface [34].
Those results were further confirmed in the PL and photocurrent ana-
lysis (Fig. S4). The above characterization confirmed that our approach
in preparing close heterojunction interface is indeed effective in redu-
cing the charge transfer resistance and promoting charge separation in
the photocatalyst [35].
Y. Jia, et al. Chemical Engineering Journal 402 (2020) 126193

Fig. 5. CO2 adsorption isotherms (a), CO-TPD (b), and CH4-TPD (c) profiles, optimized geometry structures and binding energies for CO2 (d), CO (e) and CH4 (f)
adsorption on α-Fe2O3, SnFe2O4, and SnFe2O4/α-Fe2O3.

As a result of the improved structural, optical, and the electro- photocatalyst, in addition to choosing component materials with ap-
chemical property, Octa-SnFe2O4/α-Fe2O3 can deliver higher evolution propriate band structures, the realization of a low resistance close
rate of CO(2.87 μmol/g/h) and CH4 (0.64 μmol/g/h), with 14.35-fold contact at the heterojunction interface favoring the charge migration
and 7.11-fold enhancements compared with SnFe2O4/α-Fe2O3 (M), and and separation is equally critical.
with 2.33-fold and 5.33-fold enhancements compared with SnFe2O4/α-
Fe2O3 (H) (Fig. 8f). The above comparison results indicated that to
achieve high charge carrier separation in a heterojunction

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Y. Jia, et al. Chemical Engineering Journal 402 (2020) 126193

Fig. 6. UPS spectrum (a), XPS valence spectrum (b), and bandgap energies (c) of purchased α-Fe2O3, Octa-SnFe2O4. DMPO spin-trapping ESR spectra recorded for %
O2− (d) and %OH (e) for purchased α-Fe2O3, Octa-SnFe2O4, and Octa-SnFe2O4/α-Fe2O3 under visible light, the band energy alignment and Z-scheme photocatalytic
system (f).

4. Conclusions
In summary, for the first time the Octa-SnFe2O4/α-Fe2O3 hetero-
junction photocatalyst with close contact has been successfully con-
structed by a facile solvothermal method and subsequent thermal
treatment. Structural, optical, and photoelectrochemical characteriza-
tions demonstrated that the large area close contact at the Octa-
SnFe2O4/α-Fe2O3 interface not only preserved the redox ability of the
two component materials but also significantly boosted the charge
transfer and separation in the photocatalyst. As a result, the seamless
Octa-SnFe2O4/α-Fe2O3 heterojunction showed much improved photo-
catalytic CO2 reduction activity as compared to either SnFe2O4, α-
Fe2O3, or conventional SnFe2O4/α-Fe2O3 composites. This work pro-
vides a facile and effective method for the in-situ preparation of close
contacted Octa-SnFe2O4/α-Fe2O3 heterojunctions, which may sig-
nificantly stimulate the synthesis of various seamless spinel ferrite-

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Y. Jia, et al. Chemical Engineering Journal 402 (2020) 126193

Fig. 7. PL spectra (a), time-resolved PL decay (b), transient photocurrent spectra (c), EIS (d), and cyclic voltammograms (e) of purchased α-Fe2O3, Octa-SnFe2O4 and
Octa-SnFe2O4/α-Fe2O3.

based hybrid materials and their further applications as promising Acknowledgements

photocatalysts.
This research was supported by the Basic Science Research Program
Declaration of Competing Interest (2017R1D1A1B03032265, 2019R1A2C1086881) and the Nano-
Material Technology Development Program (2009-0082580) through
The authors declare that they have no known competing financial the National Research Foundation of Korea funded by the Ministry of
interests or personal relationships that could have appeared to influ- Science, ICT and Future Planning, and Natural Science of Foundation of
ence the work reported in this paper. Hubei Province, China (NO. 2019CFB225).

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Y. Jia, et al. Chemical Engineering Journal 402 (2020) 126193

Fig. 8. SEM images of SnFe2O4/α-Fe2O3 (M) (a) and SnFe2O4/α-Fe2O3 (H) (b) composite, time-resolved PL (c), SPV spectra (d), EIS (e), and average CO and CH4
production rates (f) of SnFe2O4/α-Fe2O3 (M), SnFe2O4/α-Fe2O3 (H) and Octa-SnFe2O4/α-Fe2O3.

Appendix A. Supplementary data 123172.

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