Inorganic Colloidal Perovskite Quantum Dots for Robust Solar CO2 Reduction

Article abstract of DOI:10.1002/chem.201702237

Inorganic perovskite quantum dots as optoelectronic materials have attracted enormous attention in light-harvesting and emitting devices. However, photocatalytic conversion based on inorganic perovskite halides has not been reported. Here, we have synthes

Full text of DOI:10.1002/chem.201702237

A Journal of
Accepted Article
Title: Inorganic Colloidal Perovskite Quantum Dots Realizing Robust
Solar CO2 Reduction
Authors: Jungang Hou, Shuyan Cao, Yunzhen Wu, Zhanming Gao, Fei
Liang, Yiqing Sun, Zheshuai Lin, and Licheng Sun
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10.1002/chem.201702237
COMMUNICATION
Inorganic Colloidal Perovskite Quantum Dots Realizing Robust
Solar CO Reduction
2
[
a]
[a]
[a]
[a]
[c]
[a]
Jungang Hou, * Shuyan Cao, Yunzhen Wu, Zhanming Gao, Fei Liang, Yiqing Sun, Zheshuai
[
c]
[ab]
Lin, * Licheng Sun
*
Dedication ((optional))
Abstract: Inorganic perovskite quantum dots as optoelectronic
materials have attracted enormous attention in light harvesting and
emitting devices. However, photocatalytic conversion based on
inorganic perovskite halides has not been reported. Herein, we have
synthesized colloidal quantum dots (QDs, 3−12 nm) of cesium lead
Thus, it is an urgent need to develop highly efficient and stable
visible-light photocatalysts for CO conversion.
To address the limitation of these materials for solar-to-fuel
conversion, the state-of-the-art accomplishments have been
conducted through the design of highly active photocatalysts
from the charge separation and transport, light harvesting,
2
3
halide perovskites (CsPbBr ) as newcomer photocatalytic materials.
The bandgap energies and photoluminescence (PL) spectra are
tunable over the visible spectral region by quantum size effects on
an atomic scale. The increased carrier lifetime revealed by time-
resolved PL spectra, indicating the efficient electron−hole separation
and CO
candidates for soalr CO
inorganic lead halides MAPbX
2
activation. However, it is essential to seek novel
conversion. Recently, organic-
(MA = CH NH , X = Cl, Br, and I)
2
3
3
3
as interesting optoelectronic materials are reported on highly
efficient photovoltaic devices with certified power conversion
and transfer. As expect, the CsPbBr
over 99% achieve an efficient yield rate of 20.9 μmol/g towards solar
CO reduction. This work has opened a new avenue for inorganic
colloidal perovskite materials as efficient photocatalysts to convert
CO into valuable fuels.
3
QDs with the highly selectivity
[6]
efficiencies. It is notable that methylammonium lead iodide
material has been applied to conduct photocatalytic hydrogen
2
[
6e]
generation.
However, it is instable in humid conditions as a
[
6]
2
critical environment.
As a result, fabricating inorganic
perovskite halide nanocrystals with high stability is highly
desirable and imperative for efforts to achieve highly efficient
solar CO conversion into fuels.
2
The climate change and increasing local conflict as two
important issues are rooted in the unsustainable utilization of
Inspired by these points, the inorganic perovskite halide
nanocrystals present a new class of photochemical conversion
materials with the combined advantages of outstanding
optical signatures and high stability. Especially, colloidal
semiconductor quantum dots (QDs), are being reported
intensively as the promising optoelectronic materials by virtue
[
1]
fossil fuels accompanied with release of greenhouse gas CO
The conversion of CO reduction into energy-rich chemicals
presents promise as a viable CO utilization process, not only
reducing CO emission, but also decreasing the energy
shortage. In this regard, artificial photosynthesis based the
conversion of CO and water into valuable fuels by use of
2
.
2
2
2
[
2]
2
[7]
of the quantum confinement effect. However, it is an
photocatalysts at room temperature and ambient pressure, has
been regarded as one of the most promising and compelling
strategies for simultaneously solving the energy and
essential role for the atomic-level design and control of the
size-dependent photocatalytic system by precisely colloidal
[8]
chemistry.
It is noteworthy that the cesium lead halide
[
3]
environmental problems.
To date, many UV-, or visible-light photocatalytic systems for
CO conversion have been developed by use of various
materials, such as metal oxides (e.g. TiO , Cu O, WO , Bi WO
Zn GeO , ZnGa ), nitrides (e.g. C , GaN, (Zn1+xGe)(N )),
sulfides (e.g. CdS, ZnS and Cu ZnSnS ) and phosphides (e.g.
However, the intrinsic limitations (e.g. narrow light
(
CsPbBr ) is a promising photocataytic semiconductor that
3
has a large portion of the solar spectrum and a suitable band
gap. With all of these advantages, it is rather imperative to
2
[7]
2
2
3
2
6
,
fabricate CsPbBr
forward as an ideal candidate for in-depth understanding of
size-dependent CO reduction. The bandgap energies and
photoluminescence (PL) spectra are tunable over the visible
spectral region by quantum size-effects. The increased carrier
lifetime revealed by time-resolved PL spectra, accounting for the
improved electron-hole separation efficiency. As a result, the
3 3
QDs. Herein, the CsPbBr QDs were put
2
4
2
O
4
3
N
4
2 x
O
2
4
2
[
4,5]
InP, GaP).
harvesting, complex synthesis processes and short lifetime of
photoinduced charges) have been existed in these catalysts with
[
4,5]
poor selectivity, low conversion efficiency, and low stability.
CsPbBr
conversion efficiency from solar CO
The colloidal CsPbBr QDs have been synthesized through
3
QDs with an optimum size achieve high photochemical
2
reduction reaction.
[
a]
Prof. Dr. J. Hou, S. Cao, Y. Wu, Y. Sun, Prof. Dr. L. Sun
3
State Key Laboratory of Fine Chemicals, Institute of Artificial
Photosynthesis, DUT-KTH Joint Education and Research Center on
Molecular Devices, Dalian University of Technology (DUT), Dalian
the solution phase synthesis strategy (Figure 1a) by use of
inexpensive commercial precursors, taking advantage of the
ionic nature of the chemical bonding in these compounds.
First, Cs , Pb , and Br ions were selected as ion sources to
dissolve in the system, while oleylamine (OAm) and oleic
acid (OA) were applied as surface ligands. Then, controlling
116024, China. E-mail: jhou@dlut.edu.cn
+
2+
−
[
[
b]
c]
Prof. Dr. L. Sun
Department of Chemistry, KTH Royal Institute of Technology, 10044
Stockholm, Sweden. E-mail: lichengs@kth.se
Beijing Centre for Crystal Research and Development, Technical
Institute of Physics and Chemistry, Chinese Academy of Sciences,
Beijing 100190, China. E-mail: zslin@mail.ipc.ac.cn
the reaction of Cs-oleate with a Pb(II)-halide, the CsPbBr
3
2+
+
QDs were obtained by the arrested precipitation of Cs , Pb ,
−
and Br ions (see experimental section). The XRD pattern
Supporting information for this article is given via a link at the end of
the document.
(Figure S1) for the accumulated powder sample could be
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Chemistry - A European Journal
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COMMUNICATION
3
readily indexed to pure CsPbBr phase. From TEM images
(
Figure 1bc), the average size of the cubic-shaped CsPbBr
3
o
QDs prepared at 170 C is ranged around 8.5 nm. As shown
in Figure 1d, the lattice spacing can be indexed to the (100)
and (010) planes. To check the chemical compositions, high-
resolution spectra of the core levels of Cs 3d, Pb 4f, and Br
3
7
d were recorded (Figure S2). The peaks at 723.8 eV and
37.5 eV can be attributed to the Cs 3d3/2 and Cs 3d5/2 level
[
7a]
spectra of the CsPbBr
3
QDs.
Besides, the peaks at 138.6
eV and 143.9 eV can be indexed to the Pb 4f7/2 and Pb 4f5/2
[
7a]
level spectra of the CsPbBr
3
QDs.
In addition, the peak at
6
8.5 eV can be indexed to the Br 3d core level spectra of the
[
7a]
CsPbBr
3
QDs.
These results exhibits that the Cs, Pb, and
Br atoms are effectively and uniformly incorporated into the
CsPbBr QDs.
Figure 2. TEM images of CsPbBr
sizes, (a) 3.8 nm, (b) 6.1 nm, (c) 8.5 nm and (d) 11.6 nm.
3
QDs with different particle
3
Figure 3. Quantum-size effects in (a) UV-Vis absorption spectra
and (b) bandgap structures of CsPbBr
3
QDs with different
particle sizes, (i) 3.8 nm, (ii) 6.1 nm, (iii) 8.5 nm and (iv) 11.6 nm,
as well as (d) the calculated band structure and (e) calculated
densities of states diagrams of bulk CsPbBr and CsPbBr QDs.
3 3
CsPbBr
adjusting their particle size. From the UV-vis absorption spectra,
the adsorption edges of the CsPbBr QDs shifted the longer
3
QDs can be tuned over the visible spectral region by
3
wavelength in the visible light region with the increasing particle
size (Figure 3). To verify this point, the first-principle calculations
were achieved. As show in Figure 3c, the calculated the band
g 3
gap energy (E ) of the CsPbBr QDs was approximately 2.39 eV.
Figure 1. (a) Schematic of solution phase synthesis of colloidal
CsPbBr QDs. (bcd) TEM and HRTEM images and illustration
To understand the advantage of the CsPbBr
calculated densities of states (DOS) of bulk CsPbBr
3
QDs, the
and atomic
3
3
of crystalline structure of CsPbBr
yellow sphere, Br: red sphere).
3
(Cs: green sphere, Pb:
CsPbBr
characteristic with the narrow bandgap (Figure 3de/Figure S3).
In details, the upper region in valence band of the CsPbBr QDs
is constituted by the Cs-5p, Pb-6s and Br-4p orbitals and the
region in conduction band of CsPbBr QDs is composed of the
Cs-5p, Pb-6p and Br-4p orbitals. In comparison of bulk CsPbBr
with big size and severe aggregation (Figure S3), the increased
DOS at the conduction band edge compared with the bulk
counterpart, demonstrating that more photogenerated carriers
could be effectively transported to the conduction band minimum
3
QDs slab, reveal the typical semiconductor
3
Generally, the colloidal semiconductor quantum dots exhibit
[7]
the intrinsical quantum size effects. Herein, the perovskite QDs
with the tunable particle size have also been obtained by
adjusting the reaction temperatures. As shown in Figure 2, the
3
3
average sizes of the as-obtained CsPbBr
3
QDs operated at 140,
55, 170 and 185 C are ranged around 3.8±0.3, 6.1±0.3,
.5±0.3 and 11.6±0.3 nm, respectively. The size of the CsPbBr
o
1
8
3
QDs increases as the reaction temperature is increased. In this
regard, the optical absorption and photoluminescence spectra of
of the CsPbBr
3
QDs, corresponding the increased valence band
[
9]
maximum.
Therefore, the photogenerated electrons could
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Chemistry - A European Journal
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COMMUNICATION
easily be excited into the conduction band under solar light
the ideal surface area and reaction sites, facilitating the charge
irradiation, implementing the effective photochemical conversion. transfer to the surface, shortening the charge transfer pathways
In addition, the typical photoluminescence peak of the CsPbBr
3
and simultaneously suppressing the electron-hole recombination.
In general, the size decreasing behavior leads to severe
aggregation while the large size also decrease the surface
QDs shifted to longer wavelength sides when the size of QDs
was increased (Figure S4/S5). Based on above-mentioned
results, we can conclude that the quantum size-effects can
effectively regulate the band gap structure and improve the
[
7]
area, influencing the optical absorption and charge transfer
[
4,5]
and separation.
Thus, the optimization of the particle size
reduction.
optical absorption of the CsPbBr
To evaluate the roles of the CsPbBr
it is essential to drive the photochemical CO
CO photoreduction experiments were carried out in ethyl
acetate/H O system under a 300 W Xe lamp with a standard AM
.5G filter, and the predominant reaction products analyzed by
gas chromatography (GC) were CO, CH and H . The CO, CH
and H yields gradually increased with the photolysis time, and
the total yields of CO (RCO), CH (RCH4) and H (RH2) obtained in
the experiment after 8 h irradiation were 34.1±0.1, 12.2±0.1 and
3
QDs.
plays a pivot role upon the enhancement of solar CO
2
3
QDs upon photocatalysis,
conversion. The
In this ethyl acetate/water system, the water plays a role as a
proton source and ethyl acetate was chosen as the solvent due
2
[
11]
2
to high CO
to the stability of the CsPbBr
is no obvious influence upon the stability of the CsPbBr
the solvent of ethyl acetate with a small amount of water (Figure
S7). Notably, based on the calculation for solar CO reduction
(selectivity=(2RCO+8RCH4)/Relectronx100%), the selectivity for solar
CO reduction was impressively over 99%, indicating the
efficiently suppressed H generation in the ethyl acetate/water
system. In addition, there is no apparent change upon the
morphology and the crystalline structure of the CsPbBr QDs
2
solubility. A large amount of water is detrimental
QDs (Figure S7). However, there
QDs in
2
3
1
3
4
2
4
2
2
4
2
2
-
1
0
.80±0.03 μmol g , corresponding to approximately 4.3, 1.5 and
2
-1
-1
0.1 μmol g
h
4 2
of the formation rates of CO, CH and H ,
respectively (Figure 4a). All the product generation presents the
almost linear growth with the increased time. According to the
equation (Relectron=2RCO+8RCH4+2RH2), the averaged electron
3
before and after photocatalysis (Figure S8/S9), confirming the
excellent photostability in the ethyl acetate/water system, giving
prospective signs for practical solar fuels production.
-1
-1
yield (Relectron) rate for the CsPbBr
during the whole reaction. Such a high product formation rate of
the CsPbBr QDs is much larger than that of previously reported
WO , CdS, Cu S and PbS/TiO , demonstrating the superior
catalytic activity of CsPbBr
the CO and CH produced during solar CO
3
QDs is 20.9 μmol g
h
(
b)
3
3
2
2
[
4c,10]
3
QDs.
To investigate the origin of
reduction reaction,
4
2
the experiments demonstrated that there was no detectable
product generation in the dark or in the absence of catalysts. At
Ar atmosphere, a certain amount of CO and CO
2
was obtained,
[
7i]
indicating that the partial photooxidation of ethyl acetate.
1
3
Furthermore, isotope-labeling experiment with CO
through the analysis of GC–MS spectra (Figure S6). Based on
above analysis, the origin of CO and CH generated was
confirmed to come from CO under artificial irradiation with
CsPbBr QDs.
2
was used
Figure 5. Time-resolved PL decays for excitation at 370 nm of
tunable CsPbBr QDs with different particle sizes and band
diagram of solar CO reduction into fuels on CsPbBr QDs.
3
4
2
3
2
3
To gain an in-depth understanding of the photoexcited charge
separation efficiency, we resorted to the time-resolved
photoluminescence spectra for tracking in real time the charge
carrier dynamics. Through fitting the decay spectra, the lifetime
of 8.5 nm QDs (9.7±0.2 ns) is longer than that of 3.8 nm QDs
(
(
6.6±0.2 ns), 6.1 nm QDs (7.8±0.2 ns) and 11.6 nm QDs
8.9±0.2 ns). The longest PL lifetime implies the lowest charge
carrier recombination rate for 8.5 nm QDs. From the electron
dynamics perspective, it is essential to infer that such a dramatic
lifetime increase in the CsPbBr
conversion efficiency.
3
QDs accounts for the enhanced
Therefore, the critical advance is the
QDs to achieve the highest performance of CO
2
[12]
Figure 4. Solar CO
irradiation for CsPbBr
tunable CsPbBr QDs with different particle sizes.
2
reduction into fuels under 300 W Xe lamp
3
QDs, (a) 8.5 nm CsPbBr QDs and (b)
3
use of CsPbBr
conversion.
3
3
To in-depth elucidate the pertinent mechanisms of solar-
driven CO reduction, it is worthy to constructing the band
diagram of the CsPbBr QDs. From the absorbance data using
the Kubelka-Munk equation, the optical bandgap energy of the
8.5 nm CsPbBr QDs was determined to be 2.43 eV. To
determine the valence band maximum position of the as-
obtained CsPbBr QDs, ultraviolet photoelectron spectroscopy
measurement was performed (Figure S10). The valence band
maximum position was determined to be 5.5 eV with respect to
the vacuum level. From the determined optical bandgap and the
Since the colloidal quantum dots have emerged as promising
materials for this application due to the ability to tailor their
2
3
[
7]
properties through size modulation. To construct the bridge of
the quantum size-effect and solar-driven CO reduction, the
tunable CsPbBr QDs with various particle sizes have been
photoreduction tests. As shown in Figure 4b,
QDs achieved the highest yields of CO, CH
2
3
3
conducted the CO
the 8.5 nm CsPbBr
2
3
3
4
and H
nm CsPbBr
2
obtained after 8 h solar light irradiation. Frankly, the 8.5
QDs possess the strong optical absorption ability,
̶
3
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Chemistry - A European Journal
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COMMUNICATION
valence band maximum position, the conduction band minimum
C. Li, Z. G. Zou, Nano Lett. 2016, 16, 5547; c) P. Li, Y. Zhou, Z. Y.
Zhao, Q. F. Xu, X. Y. Wang, M. Xiao, Z. G. Zou, J. Am. Chem. Soc.
position was determined to be
̶ 3.1 eV with respect to the
2015, 137, 9547; d) J.G, Hou, H. J. Cheng, O. Takeda, H. M. Zhu,
vacuum level. From the determined optical bandgap and the
valence band maximum position, the conduction band minimum
and valence band maximum from the constructed band diagram
Angew. Chem. Int. Edit. 2015, 54, 8480; e) J. Hou, S. Cao, Y. Wu, F.
Liang, L. Ye, Z. Lin, L. Sun, Nano Energy 2016, 30, 59; f) L. Liang, F. C.
Lei, S. Gao, Y. F. Sun, X. C. Jiao, J. Wu, S. Qamar, Y. Xie, Angew.
Chem. Int. Ed. 2015, 54, 13971.
of the CsPbBr
3
QDs (Figure 5) corresponded to ̶ 1.03 V and 1.4
V versus the normal hydrogen electrode (NHE) at pH=0, which
[4]
a) O. K. Varghese, M. Paulose, T. J. LaTempa, C. A. Grimes, Nano. Lett.
2009, 9, 731; b) H. T. Li , X. Y. Zhang , D. R. MacFarlane, Adv. Energy
Mater. 2014, 1401077; c) X. Y. Chen , Y. Zhou , Q. Liu , Z. D. Li , J. G.
Liu , Z. G. Zou , ACS Appl. Mater. Interfaces 2012, 4 , 3372; d) J. Hou,
S. Cao, Y. Wu, F. Liang, Y. Sun, Z. Lin, L. Sun, Nano Energy 2017, 32,
[7]
is consistent with the previous reports. As a results, the
reduction potential of the CsPbBr QDs becomes more negative
3
o
o
than that of E (CO
0
2
/CO) =
̶
0.52 V vs NHE and E (CO
.24 V vs NHE, indicating that the photogenerated electrons
can react with adsorbed CO and H O to produce CO and CH
Figure 4). Currently, the photogenerated holes in the valence
band oxidize water to produce oxygen and protons via the half-
2 4
/CH ) = ̶
[
4]
359; e) Q. Liu, Y. Zhou, J. H. Kou, X. Y. Chen, Z. P. Tian, J. Gao, S. C.
2
2
4
Yan, Z. G. Zou, J. Am. Chem. Soc. 2010, 132, 14385; f) S. C. Yan, S. X.
Ouyang, J. Gao, M. Yang, J. Y. Feng, X. X. Fan, L. J. Wan, Z. S. Li, J.
H. Ye, Y. Zhou, Z. G. Zou, Angew. Chem. Int. Ed. 2010, 49, 6400; g) H.
Zhou, P. Li, J. Liu, Z. Chen, L. Liu, D. Dontsova, R. Yan, T. Fan, D.
Zhang, J. Ye, Nano Energy 2016, 25, 128; h) B. AlOtaibi, S. Z. Fan, D.
F. Wang, J. H. Ye, Z. T. Mi, ACS Catal. 2015, 5, 5342; i) S. Yan, H. Yu,
N. Wang, Z. Li, Z. Zou, Chem. Commun. 2012, 48, 1048.
(
+
̶
o
reaction H
2
O→1/2O
NHE). The in-situ formed O
2
+ 2H + 2e (E (O
2 2
/H O) = 0.82 V vs
evolution was observed in this
[
4]
2
system (Figure S11), revealing that water could efficiently act as
the electron donor of the photogenerated holes. Based on the
[
5]
a) J. Jin, J. Yu, D. Guo, C. Cui, W. Ho, Small 2015, 11, 5262; b) R. Zhou,
M. Guzman, J. Phys. Chem. C 2014, 118, 11649; c) T. Arai, S. Tajima,
S. Sato, K. Uemura, T. Morikawa, T. Kajino, Chem. Commun. 2011, 47,
thermodynamic and experimental analysis, the CO, CH
4 2
and H
generation and O evolution in this photocatalytic system
2
demonstrates that the photogenerated electrons and holes
simultaneously participated the respective reduction and
12664; d) T. Arai, S. Sato, T. Kajino, T. Morikawa, Energy Environ. Sci.
2013, 6, 1274; e) E. E. Barton, D. M. Rampulla, A. B. Bocarsly, J. Am.
oxidation reactions, hence giving prospective signs for solar CO
reduction to valuable fuels by use of the CsPbBr QDs.
2
Chem. Soc. 2008, 130, 6342.
3
[6]
a) L. C. Schmidt, A. Pertegꢀs, S. Gonzꢀlez-Carrero, O. Malinkiewicz, S.
Agouram, G. Mꢁnguez Espallargas, H. J. Bolink, R. E. Galian, J. Pꢂrez-
Prieto, J. Am. Chem. Soc. 2014, 136, 850; b) F. Zhang, H. Zhong, C.
Chen, X. Wu, X. Hu, H. Huang, J. Han, B. Zou, Y. Dong, ACS Nano
In summary, we have successfully synthesized colloidal
quantum dots of inorganic cesium lead halide perovskites. The
bandgap energies and photoluminescence spectra are tunable
over the visible spectral region by quantum size effects on an
atomic scale. The increased carrier lifetime revealed by time-
resolved PL spectra, suppressing the detrimental electron−hole
recombination, thereby accounting for the improved electron-
2015, 9, 4533; c) G. Li, Z. K. Tan, D. Di, M. L. Lai, L. Jiang, J. H. W.
Lim, R. H. Friend, N. C. Greenham, Nano Lett. 2015, 15, 2640; d) F.
Hao, C. C. Stoumpos, D. H. Cao, R. P. H. Chang, M. G. Kanatzidis, Nat.
Photonics 2014, 8, 489; e) S. Park, W. J. Chang,C. W. Lee, S. Park, H.
Y. Ahn, K. T. Nam, Nat. Energy 2016, 2, 16185.
hole separation efficiency. As a result, the CsPbBr
3
QDs with the
[7]
a) X. Li, Y. Wu, S. Zhang, B. Cai, Y. Gu, J. Song, H. Zeng, Adv. Funct.
Mater. 2016, 26, 2435; b) Y. Wang, X. Li, J. Song, L. Xiao, H. Zeng, H.
Sun, Adv. Mater. 2015, 27, 7101; c) J. Shamsi, Z. Dang, P. Bianchini, C.
Canale, F. D. Stasio, R. Brescia, M. Prato, L. Manna, J. Am. Chem.
Soc. 2016, 138, 7240; d) L. Protesescu, S. Yakunin, M. I. Bodnarchuk,
F. Krieg, R. Caputo, C. H. Hendon, G. X. Yang, A. Walsh, M. V.
Kovalenko, Nano Lett. 2015, 15, 3692; e) J. Song, J. Li, X. Li, L. Xu, Y.
Dong, H. Zeng, Adv. Mater. 2015, 27, 7162; f) J. B. Hoffman, A. L.
Schleper, P. V. Kamat, J. Am. Chem. Soc. 2016, 138, 8603; g) X. M. Li,
D. J. Yu, F. Cao, Y. Gu, Y. Wei, Y. Wu, J. Z. Song, H. B. Zeng, Adv.
Funct. Mater. 2016, 26, 5903; h) V. K. Ravi, G. B. Markad, A. Nag, ACS
Energy Lett. 2016, 1, 665; (i) Y. F. Xu, M. Z. Yang, B. X. Chen, X. D.
Wang, H. Y. Chen, D. B. Kuang, C. Y. Su, J. Am. Chem. Soc. 2017,
highly selectivity over 99% achieve an efficient yield rate of 20.9
-1
2
μmol g for solar CO reduction. This work not only provides a
deeper understanding of the electron-transfer mechanism
involved in inorganic colloidal perovskite materials as efficient
photocatalysts but also should open a new avenue and stimulate
further studies toward developing more efficient visible-light-
responsive colloidal perovskite quantum dots for CO
photoreduction utilizing solar energy.
2
Acknowledgements
139, 5660.
[
[
[
8]
F. F. Schweinberger, M. J. Berr, M. Döblinger, C. Wolff, K. E. Sanwald,
A. S. Crampton, C. J. Ridge, Frank Jäckel, J. Feldmann, M. Tschurl, U.
Heiz, J. Am. Chem. Soc. 2013, 135, 13262.
This work was supported by National Science Foundation of
China (No. 51472027, 51672034, 21110102036), National Basic
Research Program of China (973 program, 2014CB239402), the
Swedish Energy Agency, and the K & A Wallenberg Foundation.
9]
a) F. C. Lei, L. Zhang, Y. F. Sun, L. Liang, K. T. Liu, J. Q. Xu, Q. Zhang,
B. C. Pan, Y. Luo, Y. Xie, Angew. Chem. Int. Ed. 2015, 54, 9266; b) X.
D. Zhang, Y. Xie, Chem. Soc. Rev. 2013, 42, 8187.
10] a) B. J. Liu, J. Photochem. Photobio. A 1998, 113, 93; b) A. Manzi,
T.Simon, C. Sonnleitner, M. Doblinger, R. Wyrwich, O. Stern, J. K.
Stolarczyk, J. Feldmann, J. Am. Chem. Soc. 2015, 137, 14007; c) C.
Wang, R. L. Thompson, P. Ohodnicki, J. Baltrus, C. Matranga, J. Mater.
Chem. 2011, 21, 13452.
Keywords: Colloidal perovskite quantum dots • CsPbBr
quantum size effects • solar fuels • solar CO reduction
3
•
2
[
[
1]
2]
a) L. Thompson, J. T. Jr. Yates, Chem. Rev. 2006, 106, 4428; b) X. B.
Chen, S. S. Mao, Chem. Rev. 2007, 107, 2891.
[
[
11] C. M. Hansen, Hansen solubility parameters: a user's handbook, CRC
press, 2007.
a) S. C. Roy, O. K. Varghese, M. Paulose, C. A. Grimes, ACS Nano
12] a) Z. Zhang, Y. Huang, K. Liu, L. Guo, Q. Yuan, B. Dong, Adv. Mater.
2010, 4, 1259; b) T. Sakakura, J. C. Choi, H. Yasuda, Chem. Rev. 2007,
2015, 27, 5906; b) H. Xu, J. Hu, D. Wang, Z. Li, Q. Zhang, Y. Luo, S.
107, 2365.
Yu, H. Jiang, J. Am. Chem. Soc. 2015, 137, 13440.
[
3]
a) W. G. Tu, Y. Zhou, Z. G. Zou, Adv. Mater. 2014, 26, 4607; b) H. J. Li,
Y. Y. Gao, Y. Zhou, F. T. Fan, Q. T. Han, Q. F. Xu, X. Y. Wang, M. Xiao,
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Chemistry - A European Journal
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COMMUNICATION
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COMMUNICATION
CsPbBr
3
quantum dots as newcomer
Jungang Hou,* Shuyan Cao,Yunzhen
Wu, Yiqing Sun, Licheng Sun*
photocatalytic materials achieve an
efficient yield rate and the highly
selectivity over 99% for solar CO
reduction.
2
Page No. – Page No.
Inorganic Colloidal Perovskite
Quantum Dots Realizing Robust Solar
CO Reduction
2
This article is protected by copyright. All rights reserved.