Preparation of a ZnIn2S4-ZnAlOxnanocomposite for photoreduction of CO2to CO

Article abstract of DOI:10.1039/d1cy00278c

Solar-driven CO₂conversion into fuels and sustainable energy has attracted increasing attention around the world. However, the efficiency of the transformation remains relatively low due to the rapid recombination of photogenerated charge carriers. In this work, we prepared a ZnIn₂S₄-ZnAlO_xnanocomposite for visible light driven CO₂reduction. The thin layered structure facilitated the photoinduced charge carrier separation and transfer, and also gave excellent adsorption ability towards CO₂molecules. Such a nanocatalyst exhibited excellent activity in visible-light driven CO₂reduction with a CO optimal formation rate of 1100 μmol g^?1h^?1, which is 5 times that over bulk ZnIn₂S₄, and the CO/H₂ratio was increased from 0.2 over bulk ZnIn₂S₄to 1.5 over the ZnIn₂S₄-ZnAlO_xcomposite.In situFT-IR experiments indicated that CO₂was reduced on ZnIn₂S₄-ZnAlO_xfollowing a COOH* pathway. This work gives insights into the mechanism of the photocatalytic CO₂reduction reaction and inspiration to construct novel heterostructure materials for application in energy and environmental catalysis.

Full text of DOI:10.1039/d1cy00278c

Catalysis
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Preparation of a ZnIn S –ZnAlO nanocomposite
2
4
x
for photoreduction of CO to CO†
2
Cite this: DOI: 10.1039/d1cy00278c
a
a
b
a
a
Yuqing Shao, Xinkui Wang, * Zhaolin Dou, Xiaoyu Liang, Xinxin Zhang,
c
a
a
b
Min Pang, Qiang Xu, Min Ji
and Min Wang
*
Solar-driven CO
the world. However, the efficiency of the transformation remains relatively low due to the rapid
recombination of photogenerated charge carriers. In this work, we prepared ZnIn –ZnAlO
nanocomposite for visible light driven CO reduction. The thin layered structure facilitated the
photoinduced charge carrier separation and transfer, and also gave excellent adsorption ability towards
CO molecules. Such a nanocatalyst exhibited excellent activity in visible-light driven CO reduction with a
CO optimal formation rate of 1100 μmol g h , which is 5 times that over bulk ZnIn S , and the CO/H
2
conversion into fuels and sustainable energy has attracted increasing attention around
a
S
2 4
x
2
2
2
−1
−1
Received 13th February 2021,
Accepted 28th March 2021
2
4
2
ratio was increased from 0.2 over bulk ZnIn
experiments indicated that CO was reduced on ZnIn
gives insights into the mechanism of the photocatalytic CO
novel heterostructure materials for application in energy and environmental catalysis.
S
2 4
to 1.5 over the ZnIn
–ZnAlO following a COOH* pathway. This work
reduction reaction and inspiration to construct
2 4 x
S –ZnAlO composite. In situ FT-IR
2
S
2 4
x
DOI: 10.1039/d1cy00278c
2
rsc.li/catalysis
heterojunctions, heterophase junctions, and thin layer
Introduction
1
6–18
structures.
It is found that decreasing the thickness of
The conversion of CO into chemicals and fuels has aroused
materials can shorten the photoinduced carrier transfer
distance to the surface and thus inhibits their recombination
in the bulk phase. Construction of a thin layer two-
dimensional structure is an efficient way to promote the
2
worldwide interest, and solar-driven CO2 reduction is a
1–6
promising route and has attracted increasing attention.
During the past few decades, great efforts have been devoted
to developing various photocatalysts with different structures
efficiency of CO photoreduction.
2
7
–9
for efficient CO
2
photoreduction.
However, the
2 4
ZnIn S is a visible light responsive semiconductor with a
unsatisfactory separation efficiency of photogenerated charge
carriers is one of the most critical issues that remarkably
conduction band of −1.0 eV, and could be used as a
photocatalyst for CO reduction under visible light. Bulk
2
restricts
photocatalysts.
the
performance
During the photocatalytic process,
of
semiconductor
2 4
ZnIn S itself showed low activity due to easy recombination
of holes and electrons in the bulk. The construction of
1
0–13
19
−
+
photoinduced carriers, electrons (e ) and holes (h ),
recombined much faster than their migration from the bulk
to the surface, therefore resulting in low efficiency.
ZnIn S @CNO and the ZnIn S –In O composite promoted
2
4
2
4
2 3
the carrier separation and increased the activity, but needs
1
4,15
2+
20,21
To
Co(bpy)3 as a cocatalyst.
Recently, immobilization of
overcome these drawbacks, various strategies have been
developed to inhibit the recombination of photogenerated
holes and electrons, such as the construction of
CeO on ZnIn S increased the CO generation rate from 95 to
2
2
4
−1
−
1
180 μmol g h , but hydrogen is more easily produced with
2
2
a CO/H ratio of about 0.3, lowering the quantum yield.
2
In this paper, we report a ZnIn S –ZnAlO nanocomposite
2
4
x
for the photocatalytic reduction of CO
2
x
to CO. ZnAlO was
used to exfoliate and stabilize a ZnIn2S4 nanosheet. A thin
a
layer of ZnIn S was in situ grown on ZnAlO . Moreover, the
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian
2
4
x
University of Technology, Dalian 116024, China. E-mail: wangxinkui@dlut.edu.cn
ZnAlO
x
material gives abundant active sites for CO
2
b
Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian
adsorption. This ZnIn S –ZnAlO nanocomposite reduced the
bulk-to-face diffusion length to accelerate the separation of
charge carriers and favor CO adsorption, therefore
2
4
x
1
16024, China. E-mail: wangmin@dlut.edu.cn
c
Institute of Materials, China Academy of Engineering Physics, Mianyang 621907,
China
2
facilitating the conversion of CO2 to CO, and suppressed
†
Electronic supplementary information (ESI) available. See DOI: 10.1039/
d1cy00278c
hydrogen generation. The optimal yield of CO over ZnIn S –
2
4
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−
1
−1
ZnAlO reaches up to 1100.5 μmol g h , which is 5 times
x
that over bulk ZnIn S , and the CO/H ratio was increased
2
4
2
from 0.2 over bulk ZnIn
composite.
2
S
4
2 4 x
to 1.5 over the ZnIn S –ZnAlO
Results and discussion
General characterization of the catalysts
2 4 x
The ZnIn S –ZnAlO nanocomposite was prepared via in situ
growth on ZnAlO . The XRD results showed that several
x
phases exist in the ZnAlOx sample, including Zn(OH)2,
2 4 3 4 3 2
AlOOH, ZnAl O and Zn (OH) (NO ) . As shown in Fig. S1,†
the peak at 36.8° can be attributed to the ZnAl O phase
2
4
(
JCPDS card No. 05-0669). The peaks at 19.4°, 32.8° and 61.9°
corresponded to (001), (100) and (111) facets of Zn(OH)
respectively (JCPDS card No. 24-1444). The peaks at 28.8°,
8.5°, 42.7° and 69.8° corresponded to the (110), (200), (111)
and (130) facets of AlOOH, respectively (JCPDS card No. 54-
036). The peak at 12.8° can be attributed to Zn (OH) (NO )
3 2
2
,
3
0
3
4
(
JCPDS card No. 52-0627). The (311) plane of cubic ZnAl O
2 4
and the (200) and (111) planes of AlOOH were observed in
2
3
the TEM images (Fig. S2†). ZnIn S shows typical peaks at
2
4
2
0.5°, 27.4° and 47.4° (JCPDS card No. 72-0773). In the XRD
pattern of ZnIn –ZnAlO , there are three main peaks at
1.4°, 27.8° and 47.5°, which are assigned to the (006), (102)
and (110) crystal facets of hexagonal ZnIn S , respectively.
2
S
4
x
Fig. 1 (a) TEM, (b) HADDF-STEM, and (c and d) HRTEM images and (e)
2 4 x
EDX mappings of Zn, In, S, Al, and O elements of ZnIn S –ZnAlO .
2
2
4
2 4 x
The growth of ZnIn S on ZnAlO destroyed the crystal
structure of ZnAlOx probably because Zn on ZnAlOx was
involved in the growth of ZnIn S , indicating the strong
characteristic peaks of Zn, In, S, Al and O elements, which is
consistent with the EDX elemental mapping analysis. As
depicted in Fig. 2b, the binding energies of Zn 2p3/2 and Zn
2p1/2 for ZnIn S were 1022.6 and 1046.2 eV, indicating that
2
4
interaction between ZnIn
caused the shrinkage of the crystal cells as evidenced by the
theta value shift of the peaks to a higher angle. Besides, the
FT-IR spectrum of ZnIn –ZnAlO (Fig. S3†) shows a band at
2 4 x
S and ZnAlO . This interaction
2
4
2
7
2
the chemical state of Zn was +2. As for the In 3d spectrum,
two peaks at 445.1 and 452.7 eV were ascribed to In 3d5/2 and
2
S
4
x
−
1
28
1
620 cm , which was ascribed to the stretching vibrations of
OH groups of adsorbed H O. NO from starting materials
In 3d3/2, respectively. The spectrum of S 2p can be fitted
−
into two peaks centered at 161.6 and 162.7 eV, which are
2
3
2
− 29
was introduced in ZnAlO
peaks at 1762, 1384 and 831 cm .
on the spectrum of ZnIn S –ZnAlO due to the separation of
x
as evidenced by the appearance of
assigned to S . However, the binding energies all shifted
−
1 24,25
These bands vanished
2
4
x
x
ZnAlO sheets from nitrates in the process of exfoliation.
The morphologies and microstructures of the composite
were investigated by TEM and HAADF-STEM. From
Fig. 1a and b, both TEM and STEM images show a network
structure composed of multiple thin layers with a thickness
of approximately 5 nm, rather than microspheres with a
diameter on the μm scale, which is a typical structure of bulk
ZnIn2S4 (Fig. S4†). According to Fig. 1c and d, the lattice
distances of 0.31 and 0.46 nm were ascribed to the AlOOH
(
2
110) and Zn(OH) (100) facet, 0.32 nm corresponded to the
2
6
ZnIn S (102) facet, and 0.24 nm was ascribed to the ZnAl2-
2
4
O (311) facet, consistent with the XRD result in Fig. S1.† The
4
EDX mapping images in Fig. 1(e) indicate the even dispersion
of Zn, In, S, Al and O elements.
To unveil the elemental states and chemical properties of
the samples, X-ray photoelectron spectroscopy (XPS) was
employed on ZnIn S –ZnAlO and ZnIn S . From the survey
2
4
x
2
4
Fig. 2 (a) XPS survey spectra of ZnIn S –ZnAlO and ZnIn2S4 and (b–d)
2
4
x
spectrum in Fig. 2a, the spectrum of ZnIn S –ZnAlO shows
high-resolution spectra of Zn, In and S.
2
4
x
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negatively after ZnIn S and ZnAlO were combined. The Zn
and ZnAlOx shows a much lower CO yield, which further
suggests the intimate and strong interaction between ZnIn2S4
and ZnAlO (Fig. 3b, column 1). When Ar was used instead of
x
2
4
x
(
2p3/2: 1022.2 eV, 2p1/2: 1045.6 eV), In (3d5/2: 444.9, 3d3/2
52.4 eV) and S (2p3/2: 161.4 eV, 2p1/2: 162.5 eV) binding
energies of ZnIn S –ZnAlO are 0.6, 0.3 and 0.2 eV lower than
:
4
CO , no CO was yielded, indicating that CO was formed by
2
4
x
2
those of bulk ZnIn S , respectively. The shift of Zn, In and S
binding energies suggests the existence of intimate interfaces
CO2 reduction (Fig. 3b, column 2). Furthermore, when the
experiment was carried out in the dark, the yield of CO and
2
4
between ZnIn2S4 and ZnAlO , which is beneficial for fast
H clearly decreased (Fig. 3b, column 3). In addition, when
2
x
separation and transportation of photo-induced charge
carriers.
the experiment was conducted in the absence of a catalyst or
TEA, no significant product was detected, which suggests the
crucial role of TEA as an electron donor (Fig. 3b, column 4–
3
0
5
). The reaction can be carried out under UV-light
Photocatalytic CO reduction performance
2
illumination and the CO yield reaches above 10 000 μmol
gZnIn2S4
−
1
−1
The CO2 photoreduction reaction was carried out in an
h
(Fig. 3b, column 6), which is in line with the
acetonitrile/H O system with triethylamine (TEA) as the
electron donor under atmospheric CO and visible light (455
2
stronger absorption in the UV-light region. This is further
confirmed by the UV-vis DRS spectrum in the following
2
nm) irradiation. Fig. 3a shows the catalytic performance of
section. The volume ratio of MeCN to H O was also
2
ZnAlO and ZnIn S –ZnAlO with different ZnIn S contents.
investigated and the optimal ratio was determined to be 9 : 1,
as shown in Fig. 3c. The decrease of water content would
reduce the competitive reaction of hydrogen evolution and
x
2
4
x
2 4
ZnAlO
x
2
itself did not possess the ability to reduce CO to CO.
The highest CO yield (1100.5 μmol per gram ZnIn2S4 per
hour) was obtained on the ZnIn S –ZnAlO catalyst with 40
increase the CO/H
2
ratio. Long-term experiments were carried
–ZnAlO showed
2
4
x
wt% content, while the H
2
yield was significantly suppressed
out in the scale-up system, and 40%-ZnIn
2
S
4
x
as well. The H yield on 60%-ZnIn S –ZnAlO and 80%-ZnIn -
durable photoreduction activity with an accumulated CO
yield of 517.8 μmol. When the catalyst was used in stability
tests, the yield of CO showed a slight decrease in each cycle
(Fig. S5†), which is probably due to the photocorrosion of the
2
2
4
x
2
S –ZnAlO was almost 2 and 3 times the CO yield, while the
4
x
2 2 4
CO yield was over 1.5 times the H yield on 40%-ZnIn S –
ZnAlO , which promoted the CO production and inhibited
x
3
1
the competition hydrogen generation reaction. This is
ZnIn
the excellent CO
ZnAlO nanocomposite, which is superior to those studied in
2
S
4
-based semiconductor catalyst. These results proved
probably due to the beneficial effects of 40%-ZnIn
2
S
4
–ZnAlO
x
2
photocatalytic activity of the ZnIn
2 4
S –
on the adsorption toward CO molecules, which is studied by
2
x
3
2–34
CO adsorption FT-IR experiments in the following section.
the literature.
2
The control experiment using the physical mixture of ZnIn
2
S
4
Optical and electrochemical performance
The UV-vis DRS method was adopted to give information on
the optical properties and light absorption abilities of the
samples. In Fig. 4a, ZnIn S shows strong absorption of light
2
4
with a steep decrease in the visible light region, while ZnAlO
x
Fig. 3 (a) Catalyst screening, (b) control experiments over ZnIn
ZnAlO , (c) solvent effects on ZnIn –ZnAlO
ZnIn and ZnIn –ZnAlO . Reaction conditions: 5 mg of catalyst, 0.9
mL of MeCN, 0.1 mL of H O, 0.1 mL of triethylamine, 1 bar CO , 9 W
blue LEDs (455 nm), ∼25 °C, 12 h. Scale-up reaction: 100 mg of
catalyst, 18 mL of MeCN, 2 mL of H O, 2 mL of triethylamine, 1 bar of
CO
, ∼42 °C, 72 h.
2
S
4
–
x
2
S
4
x
and (d) time course of
2
S
4
2
S
4
x
2
2
2
Fig. 4 (a) UV-vis diffuse reflectance spectra, (b) Tauc plots, (c) valence
band XPS spectra and (d) band gap structures of ZnIn and ZnAlO
2
2
S
4
x
.
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only shows absorption in the UV light region with two
3
5
absorption peaks at around 230 and 300 nm. The band gap
energies were calculated according to the Kubelka–Munk
n/2
function (αhν = A(hν − E ) , where α, h, ν, E and A stand for
g
g
the adsorption coefficient, Planck constant, light frequency,
band gap energy and a constant, respectively, and n is 1 for
the direct band gap semiconductor and 4 for the indirect
band gap semiconductor). Fig. 4b presents the band gap
energies of the two samples. The band gap energy of ZnIn
2 4
S
(
2.18 eV) is lower than that of ZnAlO (3.34 eV). The valence
x
band XPS results in Fig. 4c indicate that the valence band of
ZnIn (1.31 eV) is lower than that of ZnAlO (2.57 eV).
2
S
4
x
According to the equation: Eg = EVB − ECB, the conduction
band positions of ZnIn S and ZnAlO were calculated to be
2 4 x
Fig. 6 In situ FT-IR spectra of ZnIn S –ZnAlO .
2
4
x
−
0.87 and −0.77 eV, respectively. Given the analysis above, the
band structures of the samples are presented in Fig. 4d. The
results indicate that ZnIn S is the photoactive species under
−
can be assigned to bidentate bicarbonate (b-HCO ) and
2
4
3
2
−
22
visible light irradiation and ZnAlO
visible light.
x
cannot be excited by
bidentate carbonate (b-CO
3
), respectively. The peaks at
−
1
−
1532 and 1260 cm can be ascribed to formate (COO ),
In order to investigate the chemical behavior of
photogenerated electron–hole pairs, we conducted
electrochemical tests on ZnIn2S4 and ZnIn S –ZnAlO . The
2
which suggests that CO reduction followed a COOH*
pathway.
3
7,38
2 4
x
transient photocurrent responses were recorded to study the
behavior of photogenerated electron–hole pairs. As shown in
Fig. 5a, ZnIn S –ZnAlO shows higher photocurrent density
Conclusions
In summary, we synthesized a ZnIn S –ZnAlO thin-layer-
2
4
x
2
4
x
than bare ZnIn
2
S
4
, which suggests a more efficient separation
structure nanocomposite for efficient visible-light driven CO2
conversion to CO. TEM and XRD results indicate the
successful combination of the ZnIn S nanosheet and ZnAlO
of photoinduced electron–hole pairs. The separation–
recombination of photogenerated charge carriers was studied
by PL spectra (Fig. 5b). The strong emission at about 603 nm on
2
4
x
layer structure. ZnAlO was used to stabilize ZnIn S for the
x
2 4
the spectrum of ZnIn
photogenerated electron–hole pairs. However, the luminescence
emission of ZnIn –ZnAlO is weaker, indicating a more
2
S
4
is produced by the recombination of
adsorption of CO
2
.
2 4 x
Moreover, the ZnIn S –ZnAlO
nanocomposite reduces the bulk-to-face diffusion path
length, and therefore accelerating the separation of
photoinduced charge carriers, which is proved by transient
photocurrent responses and PL spectra. The formation rate
of CO reaches up to 1100 μmol g
temperature and atmospheric CO pressure. CO
S
2 4
x
36
efficient separation of electron–hole pairs.
−
1
−1
h
at ambient
2
adsorption
CO adsorption properties
2
2
In order to further investigate the adsorption ability of the
FT-IR experiments revealed that the reaction followed a
composite towards CO , we employed in situ CO adsorption
COOH* pathway. This work will provide insights into
2
2
FT-IR on ZnIn
2
S
4
–ZnAlO
x
. From Fig. 6, it can be noted that
2
photocatalytic CO reduction for wider applications in the
when CO2 was not injected to the system, the background
spectrum was a straight line. After the injection of pure CO2
gas, several peaks were observed as the characteristic
photoreduction field.
Experimental
Materials
−
1
adsorption peaks of CO . The peaks at 1618 and 1359 cm
2
Zn(NO
3
)
2
·6H
2
O
(99.0%),
ZnSO
4
·7H
2
O
(99.5%),
and
hexamethylenetetramine (99.0%) were purchased from
Tianjin Damao Corporation, Al(NO ) ·9H O (99.0%) was
3
3
2
purchased from Aladdin Corporation, InCl
was purchased from Energy Chemical, thioacetamide (TAA,
9%) was purchased from Macklin Reagent Company,
3 2
·4H O (99.9%)
9
isobutyl alcohol (99%) was obtained from Tianjin Kermel
Chemical Reagent Development Center, China, and
triethylamine (TEA, 99%) was purchased from Xilong
Scientific Corporation. Deionized water used in all
experiments was obtained from a Milli-Q system (Millipore).
All reagents were used without further purification.
Fig. 5 (a) Transient photocurrent responses and (b) PL emission spectra
of ZnIn and ZnIn –ZnAlO ; excitation wavelength: 400 nm.
S
2 4
S
2 4
x
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Synthesis of ZnAlOx
then exposed to pure CO gas and adsorption spectra were
2
recorded at intervals.
ZnAlO
x
was prepared by a hexamethylenetetramine hydrolysis
3
9
method according to the literature. 0.20 mol Zn(NO ) ·6H -
O, 0.10 mol of Al(NO
3
2
2
Electrochemical tests
3
)
3
·9H
2
O
and 0.26 mol of
hexamethylenetetramine were dissolved in 200 mL deionized
water, then placed into an autoclave with Teflon-lining,
which then placed into an oven at 140 °C for 9 h. The
product was centrifuged, washed thoroughly with deionized
water, and dried at 60 °C overnight. The final product was
The electrochemical tests were conducted on an
electrochemical workstation (Corrtest CS2350H). A three-
electrode system with a platinum-plate electrode as the
counter electrode and a saturated calomel electrode (SCE) as
the reference electrode was used for measurements. Na SO
2
4
labeled ZnAlO
x
.
(0.5 M) was used as the electrolyte solution. The working
electrode is fluorine-tin oxide (FTO) coated with the sample
−
1
(
the slurry of the suspension: 10 mg mL concentration and
Synthesis of ZnIn S –ZnAlO
x
2
4
ethanol/H O acts as a solvent).
2
ZnIn S –ZnAlO was prepared with a hydrothermal method.
2
4
x
x
Typically, 254.0 mg of as-prepared ZnAlO was dispersed in 30
mL isopropyl alcohol in a 100 mL beaker, followed by magnetic
Photocatalytic CO
2
reduction
reduction was performed in a home-
The photocatalytic CO
built LED photoreactor. Typically, 5 mg of catalyst, 0.9 mL of
acetonitrile (MeCN), 0.1 mL of H O and 0.1 mL of
2
stirring for 2 h. Then 115.0 mg of ZnSO ·7H O, 234.6 mg of
4
2
InCl
CTAB) were added to the above solution and stirred for 30 min
followed by addition of an excess amount of thioacetamide
TAA) (180.3 mg). The mixture was stirred for another 30 min,
3 2
·4H O and 100 mg of cetyltrimethylammonium bromide
2
(
triethylamine (TEA) were added into a 6.5 mL quartz tube as a
photoreactor. 9 W LEDs centered at 455 nm were used as light
sources. Before irradiation, high purity CO2 gas was
introduced into the photoreactor for 30 s. During the
photoreduction process, the reactants were magnetically
stirred for 12 h and the temperature of the reaction system
was kept at 25 °C. After the reaction, the gas sample was
analyzed using a gas chromatograph (GC7890, Shanghai
Tianmei Co., Ltd., China) equipped with a TDX-01 column
and a thermal conductivity detector (TCD), and pure He was
used as an internal standard. In a scale-up reaction, 100 mg
(
and then transferred to a 100 mL stainless Teflon-lined
autoclave, tightly sealed and placed in a 160 °C oven for 20 h.
The autoclave was then naturally cooled to room temperature.
The product was washed with absolute ethanol (3 × 40 mL) and
deionized water (3 × 40 mL). After being dried in a vacuum at
6
2 4 x
0 °C for 12 h, a yellow solid was obtained as ZnIn S –ZnAlO .
General characterization
of catalyst, 18 mL MeCN, 2 mL of H O and 2 mL of TEA were
added into a 200 mL quartz photoreactor and a 300 W Xe
lamp was used as a light source. Before irradiation, the
X-ray diffraction patterns (XRD) were obtained with a
Smartlab 9 kW (Rigaku Corporation) diffractometer, using
Cu-Kα radiation at 45 kV and 200 mA. High-angle annual
dark-field scanning transmission electron microscopy
2
reactor was purged with pure CO gas five times. The pressure
2
was kept at atmospheric pressure when the purge was
finished. 5 mL of pure He was then injected to the system as
an internal standard. After that, the light was switched on
and the temperature of the system was kept below 42 °C. The
gas product was taken and detected by GC at intervals.
(
(
HAADF-STEM) images and energy dispersive spectroscopy
EDS) elemental mapping of the samples were recorded with
a JEOL JEM-2100F microscope operated at 200 kV. X-ray
photoelectron spectroscopy (XPS) and valence band XPS (VB-
XPS) analysis were performed with an ESCALAB250Xi
(
Thermo, USA) using Al Kα (1486.6 eV) as the excitation
Conflicts of interest
source. The binding energies of Zn 2p, In 3d and S 2p were
calibrated according to C 1s (284.6 eV). UV-vis diffuse
reflectance spectra (UV-vis DRS) were recorded on a UV-vis
spectrophotometer (Agilent UV-550) at room temperature in
There are no conflicts to declare.
Acknowledgements
4
the range of 200–800 nm with BaSO as the background.
Photoluminescence (PL) emission spectra were obtained with
a luminescence spectrometer from Hitachi F7000 at an
excitation wavelength of 400 nm. Fourier transform infrared
We are grateful for financial support from the National
Natural Science Foundation of China (21978032, 21676045,
21770643, 21802131), the Natural Science Foundation of
(
(
FT-IR) spectroscopy and in situ Fourier transform infrared
In situ FT-IR) spectroscopy were conducted on a Nicolet iS10
Liaoning Province (201602169) and the Fundamental
Research Funds for the Central Universities (DUT18LK34,
DUT19TD28).
IR spectrometer equipped with an MCT/A detector. For CO
2
adsorption, the samples were first treated in an FT-IR cell in
a vacuum at 150 °C for 0.5 h then cooled to room
temperature. After pretreatment, a background spectrum was
recorded at a resolution of 4 cm and then subtracted
automatically from the subsequent spectra. Each sample was
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−
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