Embedding CsPbBr3quantum dots into a pillar[5]arene-based supramolecular self-assembly for an efficient photocatalytic cross-coupling hydrogen evolution reaction

Article abstract of DOI:10.1039/d1ta00483b

Light-harvesting is a key step in photosynthesis, but it is still a challenge to create an efficient artificial light harvesting system in a broader solar spectrum to mimic natural processes. Here, we have fabricated, for the first time, a highly efficient artificial light-harvesting system through directly embedding CsPbBr₃quantum dots (QDs) inside a supramolecular self-assembly of thymine functionalized-pillar[5]arene (PTY) and an eosin Y-based derivative (EYB). The donor CsPbBr₃QDs exhibit a broad spectral absorption in the UV-visible range, and their emission shows good spectral overlap with the absorption of EYB, thus effective excitation energy is transferred from CsPbBr₃to the acceptor EYB with an energy transfer efficiency of 96.5%. Importantly, the combination displayed excellent photocatalytic activity in cross-coupling hydrogen evolution reactions, and the product yield was more than 2.5 times that obtained using eosin Y alone. Our research opens up a new avenue for utilizing perovskite QDs with broad spectral absorption as the energy donor to construct efficient light-harvesting systems for solar energy conversion.

Full text of DOI:10.1039/d1ta00483b

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PAPER
Embedding CsPbBr3 quantum dots into a pillar[5]
arene-based supramolecular self-assembly for an
efficient photocatalytic cross-coupling hydrogen
evolution reaction†
Cite this: J. Mater. Chem. A, 2021, 9,
10180
c
Kaipeng Zhong,a Siyu Lu,
Fenjuan Chen,
Wenting Guo,a Junxia Su,a Shihao Sun,a Jun Hai,a
*
a
b
a
*
*
Aiqin Wang
and Baodui Wang
Light-harvesting is a key step in photosynthesis, but it is still a challenge to create an efficient artificial light
harvesting system in a broader solar spectrum to mimic natural processes. Here, we have fabricated, for the
first time, a highly efficient artificial light-harvesting system through directly embedding CsPbBr3 quantum
dots (QDs) inside a supramolecular self-assembly of thymine functionalized-pillar[5]arene (PTY) and an
eosin Y-based derivative (EYB). The donor CsPbBr3 QDs exhibit a broad spectral absorption in the UV-
visible range, and their emission shows good spectral overlap with the absorption of EYB, thus effective
excitation energy is transferred from CsPbBr3 to the acceptor EYB with an energy transfer efficiency of
96.5%. Importantly, the combination displayed excellent photocatalytic activity in cross-coupling
hydrogen evolution reactions, and the product yield was more than 2.5 times that obtained using eosin Y
alone. Our research opens up a new avenue for utilizing perovskite QDs with broad spectral absorption
as the energy donor to construct efficient light-harvesting systems for solar energy conversion.
Received 18th January 2021
Accepted 29th March 2021
DOI: 10.1039/d1ta00483b
rsc.li/materials-a
interest because they can absorb light across a wide spectral
window.4 Among them, there is growing interest in the utiliza-
1. Introduction
tion of perovskite QDs as light harvesting materials due to their
high extinction coefficient, high quantum yield, broad spectral
absorption, and the potential for hot electron injection and
multiple exciton generation, which can enhance the light
capturing ability of organic dyes (the acceptor) through the
uorescence resonance energy transfer (FRET) process.5
However, using perovskite QDs as an energy donor to construct
highly efficient articial light harvesting systems to mimic
chlorosomes is still a challenge.
Pillar[n]arenes, as a type of pillar-shaped macrocyclic hosts,
have undergone a rapid development in the area of supramo-
lecular chemistry because of their symmetrical architecture,
unique rigid, and easily modied properties.6 The electron-rich
cavity and different kinds of driving forces that lead to the
formation of self-assemblies7–9 have enabled pillar[n]arenes to
be successfully used in the construction of a variety of inter-
esting supramolecular systems, such as nanotheranostics,
chemosensors, molecular machines, and supramolecular poly-
mers.10 More importantly, the various driving forces also
provide good opportunities to construct a tunable supramo-
lecular articial light-harvesting system.11 We envisaged that
rational introduction of perovskite QD donors and organic dye
acceptors into pillar[n]arene-based supramolecular polymers
could pave the way for the construction of a highly efficient
articial light-harvesting system.
Articial light-harvesting systems with light-harvesting and
energy transfer ability have received increasing attention due to
their key role in photosynthesis and optoelectronic devices.1
Since the uorescent donor and acceptor molecules that
construct the supramolecular organization are important
parameters in these photophysical processes, a variety of mul-
tichromophoric scaffolds have been reported based on supra-
molecular chemistry in which uorophore molecules are
conned in a matrix.2 Although effective excitation-energy
transfer could be achieved through these systems, the applica-
tion of organic uorophores in light-harvesting systems is
restricted due to their inherent narrow spectral window for
light-collection and poor photostability.3
As highly prospective light harvesting materials, inorganic
nanocrystals or quantum dots (QDs) have received tremendous
aState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous
Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou University,
Lanzhou, 730000, Gansu, China. E-mail: wangbd@lzu.edu.cn
bKey Laboratory of Clay Mineral Applied Research of Gansu Province, Lanzhou
Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R.
China. E-mail: aqwang@licp.cas.cn
cGreen Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou
450000, China. E-mail: sylu2013@zzu.edu.cn
† Electronic supplementary information (ESI) available: Experimental details,
synthesis and characterization. See DOI: 10.1039/d1ta00483b
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Fig. 1 Graphical representation of the self-assembly and photocatalytic hydrogen evolution reaction process of the supramolecular polymer
CsPbBr3@PTYIEYB.
In this study, we present a novel and efficient method to was added to the above PTYIEYB assembly to obtain
construct a highly efficient light-harvesting system by intro- Pb2+@PTYIEYB. A solution of Cs-oleate was added to the
ducing lead-containing luminescent perovskite QDs into the toluene dispersion containing Pb2+@PTYIEYB and vigorously
supramolecular self-assembly of PTY and EYB for the cross- stirred, resulting in the formation of CsPbBr3@PTYIEYB. The
coupling hydrogen evolution reaction (Fig. 1). In such self-assembly process of PTYIEYB was conrmed from the 1H
a system, EYB as a guest molecule could self-assemble with PTY NMR spectrum. As shown in Fig. S7,† when equal amounts of
through host–guest interaction. The supramolecular self- PTY and EYB were mixed in CDCl3 solution, the phenyl proton
assembly of PTYIEYB contains a thymine moiety, which acts Ha from PTY shied downeld (Fig. S7b†), while the peaks of
as a coordination site for Pb2+ ion to further form CsPbBr3 QDs. the alkyl proton H1 and H2 in EYB shied greatly towards the
The CsPbBr3 QDs conned into the interlayer of PTYIEYB help upeld region (Dd ¼ ꢀ0.53 and ꢀ0.30 ppm, respectively), which
overcome the daunting but long-term unsolved issue of self- was due to the shielding effect of the pillar[5]arene with
quenching. In addition, the hydrophobic CsPbBr3 QDs as
good donors were loaded into the hydrophobic PTYIEYB
assembly, thereby achieving an efficient energy transfer process
from CsPbBr3 QDs to the nearby receptor EYB. As a result, the
resulting CsPbBr3@PTYIEYB could be successfully applied in
the photocatalytic cross-coupling hydrogen evolution reaction.
To our knowledge, this is the rst report on a light harvesting
system based on luminescent perovskite QDs.
2. Results and discussion
Schemes S1 and S2† show the detailed synthesis procedure of
compounds PTY and EYB. PTY was synthesized by sensibly
connecting a pillar[5]arene group and thymine group via an
alkyl chain. EYB was obtained by the nucleophilic substitution
reaction between eosin Y and 1,4-dibromobutane. The obtained
1
products were characterized by H NMR and ESI-MS (Fig. S1–
S6†), respectively. The PTYIEYB assembly was formed by
Fig. 2 Partial 1H NMR spectra (400 MHz, 298 K) of Pb2+@PTYIEYB in
DMSO-d6 at various concentrations: (a) 10.0 mg mLꢀ1, (b) 20.0 mg
simply mixing equimolar PTY and EYB in DMF, and then PbBr2 mLꢀ1, (c) 40.0 mg mLꢀ1, and (d) 60.0 mg mLꢀ1 (e) 80.0 mg mLꢀ1
.
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indicating that strong coordination occurred with increase of
concentration.13a At the same time, the signals of protons H5
and H6 on EYB groups underwent large eld shis, indicating
p–p stacking interactions between the xanthene groups. In
addition, a peak at 2q ¼ 23.47ꢁ corresponding to a d-spacing of
˚
3.78 A was observed in the XRD pattern of PTYIEYB (Fig. 3a
and S11†), further conrming the existence of p–p stacking in
xanthene groups.12 The coordination between Pb2+ and the N
atom of amide (–NH) was also conrmed by FT-IR spectra. As
shown in Fig. 3b, when PTY coordinated with Pb2+, the
stretching vibration absorption peaks of imide (–NH) shied
from 3348 to 3320 cmꢀ1, and a new absorption peak appeared at
415 cmꢀ1 (Fig. S12b†), further indicating that the N–Pb2+–N
coordination bond was formed.5a Meanwhile, the XPS survey
spectra in Fig. 3c reveal that Pb was present only in the
Pb2+@PTYIEYB sample. The binding energy of Pb 4f7/2 and Pb
4f5/2 peaks appeared at 138.7 and 143.5 eV, respectively
(Fig. S13b†), indicating the existence of Pb2+.5 In the N 2p XPS
spectrum, the peak of N 2p moved from 399.4 eV in the case of
PTYIEYB to 399.6 eV for Pb2+@PTYIEYB (Fig. S13a†), indi-
cating that the N atom was coordinated with Pb2+
.
For the
5b
determination of the stoichiometry between PTY and Pb2+, Job's
plot analysis was used. In this method, the total concentration
of PTY and Pb2+ was kept at 10.0 mM, and the molar ratio of Pb2+
(XM: XM ¼ [Pb2+]/{[PTY] + [Pb2+]}) was changed from 0 to 1.
Fig. S13† shows that the molar fraction of Pb2+ was 0.33, indi-
cating the formation of a 2 : 1 complex between PTY and Pb2+
(Fig. S14†).13b
Fig.
3 (a) XRD diagrams of CsPbBr3@PTYIEYB, CsPbBr3, and
PTYIEYB; (b) FT-IR spectra and (c) XPS spectra, (d) TEM images of
CsPbBr3@PTYIEYB with different magnifications; (e) HAADF image
and the corresponding STEM-EDS elemental mapping images of C, N,
O, Br and Pb in CsPbBr3@PTYIEYB.
Moreover, scanning electron microscopy (SEM) and trans-
mission electron microscopy (TEM) images showed that the
morphology changed from a brous shape in the case of
PTYIEYB to multilayer nanosheets in the case of the formed
Pb2+@PTYIEYB (Fig. S15†). As we all know, the H bond energy
in most systems is usually within 10–40 kJ molꢀ1, which is
much lower than that of the coordinate bond (90–
350 kJ molꢀ1).14 Therefore, when a certain amount of Pb2+ ions
are added to the PTYIEYB assembly, the metal coordination
bond replaces the H bond interaction, forming a stable metal
coordination polymer gel (Fig. S16†).
In situ conned growth of CsPbBr3 QDs into the PTYIEYB
assembly to form CsPbBr3@PTYIEYB was carefully investi-
gated via SEM, TEM, and XRD. As shown in Fig. S14c,† SEM
image showed that the formed CsPbBr3@PTYIEYB was
a multilayer sheet structure, and the layer thickness of
CsPbBr3@PTYIEYB signicantly increased compared with
PTYIEYB (Fig. S15†). TEM image showed that the CsPbBr3 QDs
with an average diameter of 3 nm were inserted into the sheet
structure (Fig. 3d and S15f†). HRTEM image (Fig. 3d) showed
that interplanar distances of 0.29 nm matching the spacing of
the CsPbBr3 (200) crystal surface could be easily identied. The
elemental mapping (Fig. 3e) showed that Pb, C, N, O, and Br
were evenly distributed in the multilayer nanosheet, which was
further conrmed by EDS analysis (Fig. S17†). The XRD data
(Fig. 3a) showed that CsPbBr3@PTYIEYB had both the
diffraction peaks of PTYIEYB at 23.47ꢁ and the diffraction
peaks of CsPbBr3 QDs at 14.9ꢁ, 30.1ꢁ and 33.9ꢁ, which
conrmed the formation of CsPbBr3@PTYIEYB.5
electron-rich cavities.11a The above observations indicated that
there were interactions between the alkyl moieties in EYB and
the cavities of PTY, which led to the formation of the pseudor-
otaxane PTYIEYB.11 As shown in Fig. S8,† as the concentration
of PTYIEYB increased, the signals of protons H1,2 on the alkyl
chain and H5,6 on xanthene groups of EYB underwent
substantial upeld shis, indicating that host–guest interac-
tions and p–p stacking interactions between the xanthene
groups were enhanced during the self-assembly process.12a
Meanwhile, the signal of proton He also exhibited signicant
downeld shi, indicating the intermolecular hydrogen bond
interactions. From the FT-IR spectra (Fig. S9†), the vibration
absorption peaks of –NH and –C]O in PTY appeared at 3348
and 1674 cmꢀ1, respectively. However, aer the formation of the
PTYIEYB assembly, the vibration absorption peaks of –NH
shied to 3320 cmꢀ1, and the peak of –C]O split into two peaks
at 1669 and 1772 cmꢀ1, respectively (Fig. S9†).12 The above
results indicated that there were stable intermolecular
hydrogen bonds (–N–H/O]C–) on adjacent molecules.
Next, we examined the binding of Pb2+ with the thymine
moieties of PTY through 1H NMR titration experiments in
DMSO-d6. As shown in Fig. S10,† the signal of the imide proton
gradually shied upeld as the concentration of Pb2+ was
increased. In addition, the 1H NMR of Pb2+@PTYIEYB also
offered important evidence for its self-assembly behavior. Fig. 2
shows that the signals of protons Hd also exhibited signicant
upeld shis with increasing concentration of Pb2+@PTY,
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Generally, when there is an overlap between the absorption (donor) emission at 504 nm decreases, and the EYB (acceptor)
band of the acceptor and the emission band of the donor, emission at 562 nm increases. The above result shows that the
energy transfer from the donor to the acceptor occurs in the FRET occurred from the donor to the acceptor.1,2 At a donor/
light-harvesting system. Fig. 4a shows that there was a clear acceptor ratio of 240 : 1, energy transfer efficiency was calcu-
overlap between the absorption band of eosin Y and the emis- lated to be 96.5% for EYB, showing that CsPbBr3 QDs are an
sion band of CsPbBr3 QDs. Under the excitation of 360 nm, only excellent light collecting antenna. In addition, the uorescence
CsPbBr3 QDs emitted strong uorescence, while eosin Y almost lifetime decay curve of CsPbBr3@PTY (Fig. 4c, black line) was
did not give any uorescence signal (Fig. S18a†) because there is tted as a triple exponential decay with an average lifetime of s
no absorption centered at 360 nm (Fig. S18b†). When ¼ 8.43 ns (Table S1†). Aer the formation of CsPbBr3@-
CsPbBr3@PTYIEYB was formed, the emission peaks of both PTYIEYB (Fig. 4c, red line), the uorescence lifetimes
CsPbBr3 QDs and EYB were simultaneously observed decreased to s ¼ 5.34 ns, conrming the energy transfer from
(Fig. S18c†). Since EYB itself has no detectable uorescence the CsPbBr3 donor to the EYB acceptor.16
signal under 360 nm excitation (Fig. 18c†), the uorescence of
Moreover, based on the uorescence lifetime decay curve of
EYB in CsPbBr3@PTYIEYB must be due to the energy transfer EYB (Fig. S19†), the average lifetime (s) of EYB (lex ¼ 515 nm)
of CsPbBr3 QDs. This conrms that CsPbBr3@PTYIEYB was 0.57 ns (Table S2†). Aer the formation of CsPbBr3@-
displays uorescence through energy transfer from CsPbBr3 PTYIEYB (Fig. S19b†), the uorescence lifetimes increased to s
QDs to EYB even at wavelengths where EYB has little or no ¼ 2.07 ns. And compared with EYB alone, the average uores-
absorption.15
cence lifetime of CsPbBr3@PTYIEYB was signicantly
As shown in Fig. 4b, when EYB was gradually added to the increased, providing more evidence for the energy transfer from
dispersion of CsPbBr3@PTY in toluene, the CsPbBr3@PTY the CsPbBr3 donor to the EYB acceptor15,16e Furthermore, as
shown in Fig. S20,† when CsPbBr3@PTY was gradually added to
EYB in toluene, the emission intensity of CsPbBr3@PTY at
504 nm increased, and the emission intensity of EYB at 562 nm
also increased. These data further demonstrated that efficient
FRET occurred from the donor to the acceptor.17
Recently, eosin Y has been applied as a photosensitizer to
catalyze cross-coupling hydrogen evolution reactions and C–H
arylation of heteroarenes.18 Since eosin Y has almost no
absorption in the UV region (Fig. S18b†), visible light is usually
used as the light source in photocatalytic reactions. However,
for CsPbBr3@PTYIEYB photocatalytic reactions, sunlight can
be directly used as a light source due to the strong absorption of
CsPbBr3 QDs in the UV-vis region (Fig. S18d†), in which CsPbBr3
QDs can act as an antenna to transfer energy from UV light to
eosin Y. Therefore, in the photocatalytic cross-coupling reaction
between benzothiazole 4a and diphenylphosphine oxide 5
catalyzed by CsPbBr3@PTYIEYB,
a Xe lamp simulating
sunlight was used as the light source. Fig. 4d and S21† show
that using CsPbBr3@PTYIEYB could signicantly increase the
conversion rate of 4a and the yield of 6 compared to using eosin
Y alone. Aer 12 hours of irradiation, the yield of the cross-
coupled product 6a was 83% (Table S3†). In contrast, eosin Y
alone achieved only 33% yield, and no product was detected for
CsPbBr3 (Fig. S22†). The H2 generated in the reaction was
detected by gas chromatography, which showed that
CsPbBr3@PTYIEYB displayed excellent photocatalytic activity,
and the yield of H2 was more than twice that obtained when
eosin Y alone was used (Fig. S23 and S24†). However, no product
was detected when CsPbBr3 was used alone (Fig. S25†).18d
The cross-coupling reaction between diphenylphosphine
oxide 5 and benzothiazole with electron-donating or electron-
Fig. 4 (a) Normalized absorption spectrum of eosin Y and emission
spectrum of CsPbBr3; (b) fluorescence spectra of CsPbBr3@PTY upon
excitation at 360 nm before and after the addition of EYB. The inset withdrawing groups was also examined by using CsPbBr3@-
photographs show the change in the fluorescence of CsPbBr3@PTY
PTYIEYB as the photocatalyst. As shown in Table S3,† the
and after the addition of EYB. (c) Fluorescence decay profiles of
yields of the cross-coupled products 6b, 6c, and 6d were 76%,
CsPbBr3@PTY (blank line), CsPbBr3@PTYIEYB (red line). (d) Yields of 6
78%, and 81%, respectively. The high photocatalytic activity of
CsPbBr3@PTYIEYB is due to the increased the number of
versus reaction time. (e) Plausible mechanism of the cross-coupling
hydrogen evolution reaction using CsPbBr3@PTYIEYB as the
photocatalyst.
excited photocatalysts (EYB) during FRET process. Meanwhile,
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the increased hydrogen yield provides an effective way for the tube under vigorous stirring. Next, 10 mL Cs-oleate (0.1 mmol,
conversion and storage of solar energy in the cross-coupling DMF) was slowly added dropwise to the above system to obtain
reaction. In addition, the stability of CsPbBr3@PTYIEYB was the CsPbBr3@PTYIEYB precursor. Then, a xed amount of
studied by XRD and TEM, which is essential for improving the precursor solution was dropped into toluene under vigorous
photocatalytic activity of dye photosensitizers. As shown in stirring. Aer that, a yellow-red colloidal solution was formed,
Fig. S26,† aer the photocatalyst reaction was complete, the indicating that CsPbBr3@PTYIEYB was successfully obtained.
morphology of CsPbBr3@PTYIEYB was basically maintained,
and the frame and composition of CsPbBr3@PTYIEYB were
also well maintained. All these results indicate that the
Conflicts of interest
CsPbBr3@PTYIEYB light-harvesting system exhibits high effi- There are no conicts to declare.
ciency light-harvesting and light-conversion performance.
Acknowledgements
3. Conclusions
The work was supported by the National Natural Science
Foundation of China (21977041 and 21904052), National Key
R&D Program of China (2020YFC1807302), Natural Science
Foundation of Gansu Province (20JR5RA297 and 20JR5RF611),
Key Laboratory of Clay Mineral Applied Research of Gansu
Province (CMAR-2019-1).
In summary, the rst example of a highly efficient articial
light-harvesting system was successfully fabricated based on the
in situ conned growth of CsPbBr3 QDs in the PTYIEYB
assembly. The donor CsPbBr3 QDs are used to harvest photons
in a broad spectral region, in which EYB has almost no
absorption. Therefore, such a combination can transfer energy
from CsPbBr3 QDs with much broader absorption spectra to
EYB through an efficient FRET process, and an energy transfer
efficiency of 96.5% was achieved. More importantly, in the
cross-coupled hydrogen evolution reaction, CsPbBr3@-
PTYIEYB showed excellent photocatalytic activity, and the
yield of the product was more than 2.5 times that obtained
when eosin Y alone was used. This study not only paves the way
for utilizing perovskite QDs as an energy donor to construct
efficient light-harvesting systems with greater coverage of the
solar spectrum but also offers one interesting possibility for the
utilization of perovskite QDs to synthesize useful chemical
products and chemical fuels.
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4. Experimental section
4.1 Synthesis of PTY
Synthesis of PTY: 3 (300 mg, 0.29 mmol), thymidine derivative
(81
mg,
0.44
mmol),
1-(3-dimethylaminopropyl)-3-
ethylcarbodiimide hydrochloride (84 mg, 0.44 mmol), and 4-
dimethylaminopyridine (3 mg) were added into dichloro-
methane (50 mL). Then, the resulting solution was stirred at
room temperature for 24 h. The mixture was concentrated at
reduced pressure. The crude product was puried by silica
column chromatography (dichloromethane/methanol ¼ 30 : 1)
to give a white solid (0.24 g, yield: 68%).
4.2 Preparation of supramolecular assembly solutions
The blank PTYIEYB assembly solution was prepared as
follows: EYB (10 mg) was dissolved in CHCl3 (10 mL). Subse-
quently, the above solution was added to the PTY solution
(10 mg mLꢀ1) during ultrasonication within 30 s to generate the
assembly solutions in CHCl3.
4.3 Preparation of CsPbBr3@PTYIEYB
A mixture of PTY (100 mL, 0.1 m mol), EYB (100 mL, 0.1 m mol),
and PbBr2 (10 mL, 0.1 m mol) was added to a 7 mL centrifuge
7 D. Xia, P. Wang, X. Ji, N. M. Khashab, J. L. Sessler and
F. Huang, Chem. Rev., 2020, 120, 6070–6123.
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Journal of Materials Chemistry A
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