Revealing the A-Site Effect of Lead-Free A3Sb2Br9 Perovskite in Photocatalytic C(sp3)?H Bond Activation

Article abstract of DOI:10.1002/anie.202005495

The lead-free halide perovskite A₃Sb₂Br₉ is utilized as a photocatalyst for the first time for C(sp³)?H bond activation. A₃Sb₂Br₉ nanoparticles (A₃Sb₂Br₉ NPs) with different ratios of Cs and CH₃NH₃ (MA) show different photocatalytic activities for toluene oxidation and the photocatalytic performance is enhanced when increasing the amount of Cs. The octahedron distortion caused by A-site cations can change the electronic properties of X-site ions and further affect the electron transfer from toluene molecules to Br sites. After the regulation of A-site cations, the photocatalytic activity is higher with A₃Sb₂Br₉ NPs than that with classic photocatalysts (TiO₂, WO₃, and CdS). The main active species involved in photocatalytic oxidation of toluene are photogenerated holes (h⁺) and superoxide anions (^.O₂^?). The octahedron distortion by A-site cations affecting photocatalytic activity remains unique and is also a step forward for understanding more about halide-perovskite-based photocatalysis. The relationship between octahedron distortion and photocatalysis can also guide the design of new photocatalytic systems involving other halide perovskites.

Full text of DOI:10.1002/anie.202005495

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Accepted Article
Title: Revealing the A-site effect of lead-free A3Sb2Br9 perovskite in
photocatalytic C (sp3)-H bonds activation
Authors: Zhenzhen Zhang, Yuying Yang, Yingying Wang, Lanlan
Yang, Qi Li, Langxing Chen, and Dongsheng Xu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202005495
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10.1002/anie.202005495
Angewandte Chemie International Edition
COMMUNICATION
Revealing the A-site effect of lead-free A3Sb2Br9 perovskite in
photocatalytic C (sp3)-H bonds activation
Zhenzhen Zhang,[a,b] Yuying Yang,[a] Yingying Wang,[a] Lanlan Yang,[a] Qi Li,*[a] Langxing Chen*[b] and
Dongsheng Xu*[a]
Abstract: Lead-free halide perovskite of A3Sb2Br9 is utilized as
photocatalyst for the first time to C (sp3)-H bonds activation.
A3Sb2Br9 nanoparticles (A3Sb2Br9 NPs) with different ratios of Cs and
MA show different photocatalytic activity for toluene oxidation and
the photocatalytic performance is enhanced when increasing the
amount of Cs. We reveal that the octahedron distortion caused by A-
site cations can change the electronic property of X-site ions and
further affect the electron transfer from toluene molecules to Br sites.
After the regulation of A-site cations, the photocatalytic activity is
higher with A3Sb2Br9 NPs than that with some classic photocatalysts
(TiO2, WO3 and CdS). The main active species involved in
photocatalytic oxidation of toluene are photogenerated holes (h+)
employed to improve the photocatalytic efficiency of halide
perovskites.
It is widely accepted that A-site cations are rarely
considered for the performance optimization of halide perovskite
photocatalysts because they are not directly involved in the
construction of the bandgaps[15]. Bhosale et al[16] reported that
Cs3Bi2I9 exhibited higher efficiency of carrier generation relative
to MA3Bi2I9 and Rb3Bi2I9 in photocatalytic CO2 reduction when
irradiated by light at 305 nm. However, it is unclear that the
holes and electrons are excited by either bandgap absorption of
semiconductor or Bi-I transition under such high-energy UV light
irradiation.
In this communication, we employed A3Sb2Br9 perovskite
nanoparticles (NPs) as a new photocatalyst into visible-light-
driven photocatalytic C(sp3)-H bonds activation, indicating that
the photocatalytic activity is strongly related to the distortion of
[SbBr6] octahedron affected by A-site cations. Theoretical
calculation[17] indicates that Cs3Sb2Br9 exhibits suitable band
structure (conduction band position: -3.98 V; valence band
-
and superoxide anions (•O2 ). The view of octahedron distortion by
A-site cations affecting photocatalytic activity remains unique and is
also a step forward for understanding more insights to halide-
perovskite-based photocatalysis. This opinion of relations between
octahedron distortion and photocatalysis can also guide the design
of new photocatalytic systems involved in other halide perovskites.
position: -6.58
V vs. vacuum) and obvious difference of
In recent years, lead halide perovskites with ABX3 stoichiometry
(where A = monovalent cation, B = Pb2+ and X = halide anion),
are demonstrated to be good photocatalysts because of their
high extinction coefficients[1], optimal band gaps[2], low exciton
binding energy[3] and excellent charge transport properties[4].
They have been successfully applied in several photocatalytic
reactions, e.g. hydrogen generation[5], CO2 reduction[6], dye
degradation[7] and organic synthesis[8]. However, the
photocatalysis involved in lead halide perovskites suffers from
disadvantages of low efficiency, unsatisfied stability and severe
toxicity of lead. To address these problems, lead-free
perovskites, in which Pb2+ at B-site are substituted by In3+, Bi3+,
Sb3+ or Sn4+, have been widely investigated because of their
lower toxicity and relatively higher stability[9]. Moreover,
modifications of X-site[10] and B-site[11] ions are effective ways to
optimize their bandgap structures for improving their visible-light
absorption ability and redox ability of photogenerated holes and
electrons. Besides, methods such as doping[12], cocatalyst
immobilization[13], and semiconductor combinations[6b, 14] are also
mobilities between holes and electrons, implying high oxidation
ability of its holes and high efficiency of charge separation. In
our experiments, Cs3Sb2Br9 NPs presented stable and efficient
photocatalytic ability for toluene oxidation to benzaldehyde.
Interestingly, the photocatalytic activity with pure Cs3Sb2Br9 NPs
is about 5.3 times of that with MA3Sb2Br9 NPs and the
photocatalytic efficiency of CsxMA3-xSb2Br9 NPs increases with
the increase of Cs ratio. X-ray photoelectron spectroscopy
(XPS) characterizations indicate that the binding energies of Sb
shift in the negative direction with the increase of the Cs+
amount in CsxMA3-xSb2Br9 NPs. According to the photocatalytic
performance, crystal structures and XPS results, we deduce that
the change of octahedron distortion by A-site cations can affect
the electronic property of Br active sites and lead to the disparity
of the ability of electron transfer from toluene molecules to Br
sites.
A3Sb2Br9 NPs were synthesized by an anti-solvent
recrystallization method. ABr (A=Cs or MA) and SbBr3 were
dissolved in good solvent of DMSO and quickly poured into a
mixture of chloroform and oleic acid as poor solvent. As can be
seen in Figure 1A, the size of Cs3Sb2Br9 NPs is from tens of
nanometers to hundreds of nanometers. In the HRTEM image of
Cs3Sb2Br9 NPs (Figure 1B), lattice fringes with 0.21, 0.31, and
0.40 nm spacing, corresponding to (302), (112) and (110) facets
of Cs3Sb2Br9, respectively, can be identified. The PXRD patterns
of CsxMA3-xSb2Br9 NPs (Figure 1C), in which the x values were
evaluated by ICP-AES (Table S1), display that their crystal
structures are similar to that of Cs3Sb2Br9 NPs and there is no
obvious phase segregation. With the decrease of Cs+ amount in
CsxMA3-xSb2Br9 NPs, the peaks continually shift to small angles,
attributing to the octahedron distortion by larger MA+ ions.
[a]
Dr. Z. Zhang, Y. Yang, Dr. Y. Wang, L. Yang, Prof. Dr. Q. Li, Prof.
Dr. D. Xu
Beijing National Laboratory for Molecular Sciences, State Key
Laboratory for Structural Chemistry of Unstable and Stable Species,
College of Chemistry and Molecular Engineering, Peking University,
Beijing 100871, China
E-mail address: liqi2010@pku.edu.cn
dsxu@pku.edu.cn
[b]
Dr. Z. Zhang, Prof. Dr. L. Chen
Research Center for Analytical Sciences, College of Chemistry,
Tianjin Key Laboratory of Biosensing and Molecular Recognition,
State Key Laboratory of Medicinal Chemical Biology, Nankai
University, Tianjin 300071, China
E-mail address: lxchen@nankai.edu.cn
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10.1002/anie.202005495
Angewandte Chemie International Edition
COMMUNICATION
Meanwhile, the optical absorption band edges of CsxMA3-xSb2Br9
NPs show a slight blue shift with the MA+ increasing (Figure 1D).
As the size of MA+ is larger than that of Cs+, the cell volume of
CsxMA3-xSb2Br9 increases with the adding of MA+, exhibiting
t-butanol for •OH radicals. From Figure 2C, it can be found that
-
the h+ and •O2 have positive correlation with the conversion rate
while •OH radicals are unaffected. The characteristic peaks of
-
DMPO-•O2 adduct in the EPR spectra (Figure 2D) upon visible-
-
larger bandgaps, in accordance with the reported result [15a]
.
light irradiation also proves the existence of •O2 . All these
-
results demonstrate that h+ and •O2 are main active species in
photocatalytic oxidation of toluene.
2.5
2.0
1.5
1.0
0.5
0.0
1.5
1.0
0.5
0.0
(A)
(B)
Benzaldehyde
Benzyl alcohol
1.6
1.2
0.8
0.4
0.0
300
400
500
600
700
0
0.9
1.8
2.3
2.6
3
Wavelength (nm)
x value in CsxMA3-xSb2Br9
(D)
(C)
After 4 min irradiation
2.0
1.5
1.0
0.5
0.0
Benzaldehyde
Benzyl alcohol
Dark
-
•O2
+
316 318 320 322 324 326 328 330
Magnetic field (mT)
No scavenger
•OH
h
Figure 1. SEM image (A) and TEM image (B) of Cs3Sb2Br9 NPs; PXRD
patterns (C) and optical absorption spectra (D) of CsxMA3-xSb2Br9 NPs (x = 0-
3)
Figure 2. (A) Photocatalytic activity of toluene oxidation with CsxMA3-xSb2Br9
NPs (x = 0-3) photocatalysts; (B) Optical absorption spectrum of Cs3Sb2Br9
NPs and the total production rates of benzaldehyde and benzyl alcohol at
different monochromatic incident light irradiation (light intensity: 20 mW cm-2;
irradiation time: 1 h); (C) Photocatalytic activity of toluene oxidation in the
absence or presence of various active species scavengers; (D) EPR spectra
To study the influence of A-site cations in A3Sb2Br9 NPs on
photocatalysis, photocatalytic oxidation of toluene was carried
out with CsxMA3-xSb2Br9 NPs (x=0-3). The main products are
benzaldehyde and benzyl alcohol, and their MS spectra are
shown in Figure S1. The conversion rates of toluene oxidation
are firstly enhanced and then dropped a little with the increase of
Cs+ (Figure 2A). The photocatalytic activity with pure Cs3Sb2Br9
NPs is about 5.3 times of that with MA3Sb2Br9 NPs, which cannot
be attributed to the slight narrowing (ca. 0.13 eV, Figure S2A
and S2B) of bandgaps. Meanwhile, the narrowing of bandgaps
will lift the valance band positions (XPS valance band spectra in
Figure S2C) and further lower the oxidation ability. In addition to
toluene oxidation, Cs3Sb2Br9 NPs are also efficient for
photocatalytic C (sp3)-H bonds activation in other substrates, e.g.
2-BT, 4-BT and cyclohexane (Table 1). Specially, for the
photocatalytic oxidation of cyclohexane, cyclohexanol and
cyclohexanone are produced, in contrast to single product of
cyclohexanone for FAPbBr3 photocatalyst[18]. To reveal the high
activity of Cs3Sb2Br9 NPs, photocatalytic experiments under
monochromatic light irradiation were conducted (Figure 2B). The
total amount of benzaldehyde and benzyl alcohol products at
monochromatic light can be well fitted with the optical absorption
spectrum of Cs3Sb2Br9 NPs, indicating a photocatalytic oxidation
mechanism. As shown in Figure S3, the photocatalytic toluene
-
of DMPO-•O2 adduct in the dark (black curve) and under the irradiation of
visible light for 4 min (red curve)
Table 1 Photo-oxidation of hydrocarbons over Cs3Sb2Br9 NPs photocatalyst
under visible light irradiation in O2 atmosphere [a]
Production rate
(mmol g-1 h-1)
Substrates [b]
Products [c]
Benzaldehyde
Benzyl alcohol
c-Hexanol
c-Hexanone
2-BBD
1.98
0.54
0.70
0.28
1.76
0.52
2.07
Toluene
c-Hexane
2-BT
2-BBA
4-BBD
4-BT
4-BBA
0.50
[a]
Reaction conditions: 5 mL liquid hydrocarbon, 10 mg Cs3Sb2Br9 NPs as
photocatalyst, 1 atm O2 at room temperature under visible light (λ＞420 nm)
irradiation, reaction time: 4 h
[b] c-Hexane: cyclohexane; 2-BT: 2-bromotoluene; 4-BT: 4-bromotoluene
oxidation
can
be
severely
blocked
by
2,2’,6,6’-
[c]
tetramethylpiperidine-1-oxyl (TEMPO), proving that the
photocatalytic toluene oxidation is a free-radical-based process.
Moreover, experiments with specific scavengers were conducted
to verify the roles of various redox-active species, e.g.,
ammonium oxalate for holes (h+), 1,4-benzoquinone for •O2- and
c-Hexanol: cyclohexanol; c-Hexanone: cyclohexanone; 2-BBD: 2-
bromobenzaldehyde;
bromobenzaldehyde; 4-BBA: 4-bromobenzyl alcohol
2-BBA:
2-bromobenzyl
alcohol;
4-BBD:
4-
To elucidate the mechanism of A-site effect in the above
photocatalytic processes, XPS analysis of CsxMA3-xSb2Br9 NPs
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10.1002/anie.202005495
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Sb 4d
was performed (Figure S4 and Figure 3). In general, A-site
cations can cause the octahedron distortion in halide perovskites
due to Jahn-Teller effect and further affect the crystal field
splitting energy of the central ions at B-sites. In Figure 3, the
binding energy of Sb 4d shifts negatively gradually as the
increase of x value in CsxMA3-xSb2Br9 NPs. In contrast, the
binding energies of N 1s, Cs 3d and Br 3d have no obvious
change (Figure S4). This indicates that Sb elements become
electron richer with the decrease of MA+ amount and Br
subsequently should be electron deficient to certain extent.
34.06 eV
35.24 eV
Cs3Sb2Br9
Cs2.6MA0.4Sb2Br9
Cs2.3MA0.7Sb2Br9
Cs1.8MA1.2Sb2Br9
Cs0.9MA2.1Sb2Br9
35.55 eV
34.31 eV
MA3Sb2Br9
40
45
35
Binding energy (eV)
30
25
Figure 3. High-resolution XPS spectra of Sb 4d for CsxMA3-xSb2Br9 NPs (x=0-
3).
Based on the analysis above, we propose the mechanisms
of both photocatalytic C (sp3)-H bonds activation and the A-site
effect in A3Sb2Br9, as shown in Figure 4. Firstly, h+ and e- are
generated on the surface of A3Sb2Br9 photocatalyst under visible
light irradiation. Then, photogenerated h+ oxidize toluene to
benzyl radicals, which is usually regarded as the rate-determing
-
step[19]; meawhile, photogenerated e- reduce O2 to •O2 . Benzyl
-
radicals and •O2 can react with each other to form
benzaldehyde and OH-, then OH- further reacts with protons on
the surface of A3Sb2Br9 NPs to produce H2O molecules. During
the above process, Br sites are responsible for the generation of
h+ and the breaking of C-H bonds[20]. Hence, the electronic
properties of Br atoms on the surface can tremendously affect
the activity of toluene oxidation. As we can see in Figure 4B,
three Sb-Br bonds become shorter and the other three become
longer for the MA3Sb2Br9 octahedron, compared to that for
Cs3Sb2Br9 octahedron (the data are obtained from the
crystallographic information files of ICSD-39824 for Cs3Sb2Br9
and ICSD-110339 for MA3Sb2Br9). In other words, there has
octahedron distortion for MA3Sb2Br9. The octahedron distortion
can be reflected by the values of c/a in unit cells and smaller c/a
means larger distortion in the case of A3Sb2Br9. From Figure S5
(c/a values were calculated from the PXRD data), we can see
that the octahedron distortion of CsxMA3-xSb2Br9 becomes larger
with the increase of MA amount. Combining the XPS results and
crystal structures, we believe that electron cloud density of Br
sites on the surface of A3Sb2Br9 increases when Cs are replaced
by MA and results in decreasing the ability on the weakening of
C-H bonds.
Figure 4. Possible mechanism of A-site effect on C (sp3)-H bonds activation:
(A) photocatalytic process of toluene oxidation; (B) octahedron distortion
caused by A-site cations
Moreover, this A-site effect can be extended to direct the
design of new photocatalytic systems involved in other halide
perovskites. On one hand, for the oxidation reactions occurred
at X-site, the octahedron distortion related to A-site cations can
make X-site ions electron richer and lower the oxidation ability of
X-site ions. Similar results were observed for perovskite oxides-
based photocatalysis.[21] In our experiments, the photocatalytic
activity with Cs3Sb2Br9 NPs is about 20.7, 7.8 and 4.1 times of
that with CdS NPs, WO3 NPs and P25, respectively (Figure S6).
On the other hand, for reduction reactions at B-sites like
hydrogen evolution reaction[10], octahedron distortion is also not
beneficial for photocatalytic reactions because of the decrease
of electron cloud density at B-sites. In addition, octahedron
distortion by A-site cations can also affect the photocatalytic
stability of halide perovskites because of their weaker chemical
stability and lower electron consumption rate. As shown in
Figure S7, over 80% photocatalytic efficiency retained after four
times of cycling for Cs3Sb2Br9 NPs with higher stability. The main
structure was preserved after four cycles of reaction, and the
appearance of CsBr peaks in PXRD pattern might be
responsible for the decrease of photocatalytic activity during the
long-time reactions (Figure S8-11).
In conclusion, lead-free A3Sb2Br9 perovskites were applied
in photocatalytic applications for the first time and high
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10.1002/anie.202005495
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COMMUNICATION
photocatalytic activity for C (sp3)-H bond activation was obtained.
The main redox-active species are photogenerated holes and
superoxide anions. More importantly, it is demonstrated that A-
site cations in halide perovskites have significant effect on the
photocatalytic efficiency and the increase of Cs+ amount in
CsxMA3-xSb2Br9 photocatalyst can obviously enhance the
photocatalytic performance. We reveal that the octahedron
distortion affected by A-site cations can change electronic
properties of Br active sites and further vary the photocatalytic
capacity. This work would provide new insight for the A-site
effect in halide perovskite photocatalysis and pave new ways for
designing highly efficient halide perovskite photocatalysts.
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2018, 140, 1019-1027; dA. Wang, X. Yan, M. Zhang, S. Sun, M. Yang,
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10.1002/anie.202005495
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
A3Sb2Br9 nanoparticles (NPs)
with different ratios of Cs and
MA were employed into
photocatalytic C (sp3)-H bonds
activation with high conversion
rates. It was demonstrated that
the octahedron distortion by A-
site cations could affect the
electronic property of A3Sb2Br9
and further influence the
photocatalytic activity.
Zhenzhen Zhanga, b, Yuying
Yanga, Yingying Wanga, Lanlan
Yanga, Qi Li a*, Langxing Chenb*,
Dongsheng Xua*
Page No. – Page No.
Revealing the A-site effect of
lead-free A3Sb2Br9 perovskite
in photocatalytic C (sp3)-H
bonds activation
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