Hydrogen Peroxide Involved Anodic Charge Transfer and Electrochemiluminescence of All-Inorganic Halide Perovskite CsPbBr3 Nanocrystals in an Aqueous Medium

Article abstract of DOI:10.1021/acs.inorgchem.7b01515

Reactive oxygen species (ROS) involved anodic charge transfer and electrochemiluminescence (ECL) of all-inorganic halide perovskite CsPbBr₃ nanocrystals (NCs) were investigated in an aqueous medium with hydrogen peroxide (H₂O₂) as the model. CsPbBr₃ NCs could be electrochemically oxidized to positively charged states by injecting holes onto the highest occupied molecular orbitals and could be chemically reduced to negatively charged states by injecting electrons onto the lowest unoccupied molecular orbitals by ROS. The charge transfer between CsPbBr₃ NCs of oxidative and reductive states could bring out monochromatic ECL with onset around +0.8 V, maximum emission around 519 nm, and a full width at half-maximum around 20 nm. H₂O₂ could selectively enhance the anodic ECL of CsPbBr₃ NCs, which not only opened a way to design a bioprocess-involved photovoltaic device with CsPbBr₃ NCs but also was promising for color-selective ECL biosensing.

Full text of DOI:10.1021/acs.inorgchem.7b01515

Communication
pubs.acs.org/IC
Hydrogen Peroxide Involved Anodic Charge Transfer and
Electrochemiluminescence of All-Inorganic Halide Perovskite
CsPbBr3 Nanocrystals in an Aqueous Medium
Yan Huang,†,§ Xiaoyan Long,‡,§ Dazhong Shen,⊥ Guizheng Zou,*,‡ Bin Zhang,‡
and Huaisheng Wang*,†
†Department of Chemistry, Liaocheng University, Liaocheng 252059, China
‡School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
⊥College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China
S
* Supporting Information
ABSTRACT: Reactive oxygen species (ROS) involved
anodic charge transfer and electrochemiluminescence
(ECL) of all-inorganic halide perovskite CsPbBr3 nano-
crystals (NCs) were investigated in an aqueous medium
with hydrogen peroxide (H2O2) as the model. CsPbBr3
NCs could be electrochemically oxidized to positively
charged states by injecting holes onto the highest occupied
molecular orbitals and could be chemically reduced to
negatively charged states by injecting electrons onto the
lowest unoccupied molecular orbitals by ROS. The charge
transfer between CsPbBr3 NCs of oxidative and reductive
states could bring out monochromatic ECL with onset
around +0.8 V, maximum emission around 519 nm, and a
full width at half-maximum around 20 nm. H2O2 could
selectively enhance the anodic ECL of CsPbBr3 NCs,
which not only opened a way to design a bioprocess-
involved photovoltaic device with CsPbBr3 NCs but also
was promising for color-selective ECL biosensing.
Figure 1. UV−vis absorption and PL (λex = 400 nm) spectra of CsPbBr3
NCs. Insets: (A) Fluorescence decay curve of CsPbBr3 NCs. SEM
patterns of (B) a GCE and (C) CsPbBr3 NCs|GCE.
induced electrochemiluminescence (ECL) of CsPbBr3 NCs in an
organic medium.15 ECL is a powerful technique to explore the
charged state and charge transfer of various NCs16,17 and
especially to design novel ECL strategies with NCs as emitters.18
Although many NCs, such as CdSe,19 CdTe,20 ZnSe,21 and
CdInS,22 have been designed as promising electrochemilumino-
phores because of their ECL in an aqueous medium, few
investigations on the charge transfer and ECL of all-inorganic
perovskite NCs in an aqueous medium have been carried out
until now.23,24 Because the insolubility of CsPbBr3 NCs prohibits
NC release from CsPbBr3 NCs|GCE into an aqueous medium,
which is favorable for the improved stability of CsPbBr3 NCs,
herein we explored the anodic charge transfer and ECL of all-
inorganic perovskite NCs in an aqueous medium with CsPbBr3
NCs|GCE and found that some reactive oxygen species (ROS),
such as hydrogen peroxide (H2O2), participated in the anodic
redox and ECL of CsPbBr3 NCs. H2O2 was involved in many
bioprocesses25 and was crucial to the image function of
biomolecules under a stimulated environment. These results
he earlier researches on all-inorganic halide perovskite
T
(CsPbX3, X = Cl, Br, and I) mainly focused on bulk crystals
or thin films. Since Protesescu and co-workers proposed a
convenient method to prepare CsPbX3 nanocrystals (NCs),1
CsPbX3 NCs have become promising materials for photovoltaic
and optoelectronic devices.2−5 CsPbX3 NCs not only displayed
outstanding optical performances,5−7 such as tunable photo-
luminescence (PL), high quantum yields, and excellent color
purity,1,6,8−10 but also were promising for various expanded
applications because PL and electroluminescence of CsPbBr3
NCs were intrinsically different from those of traditional colloidal
NCs (Figure 1).7,11,12 Although an exchange reaction between
CsPbBr3 NCs and organohalides has been used to determine
ions,13 only a few fluorescent strategies have been proposed with
CsPbBr3 NCs as lumiphores;14 because perovskite NCs are
unstable in polar solvents,14 they decompose and lose PL quickly
in strong polar solvents such as water or ethanol.
Recently, our group demonstrated that CsPbBr3 NCs,
prepared by the method proposed by Protesescu and co-
workers,1 could form a perovskite NC film on a glassy carbon
electrode (GCE), i.e., CsPbBr3 NCs|GCE,15 and CsPbBr3 NCs|
GCE could be utilized to explore the electrochemical redox-
Received: June 15, 2017
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b01515
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
are important to the design of a biorelated optoelectronic device
and a novel biorelated ECL strategy.19,26,27
spectrum was almost identical with the PL spectrum of CsPbBr3
NCs, which not only confirmed that the anodic ECL originated
from CsPbBr3 NCs but also indicated that there were no surface
defects or traps on CsPbBr3 NCs of highly crystallized
structures15 because the surface defects or traps on unpassivated
NCs might result in an obvious red-shifted or broadened ECL
spectrum.29−31 The color purity of ECL from CsPbBr3 NCs|
GCE in an aqueous medium was almost the same to those in an
organic medium15 and was much higher than those from both the
traditional chemical ECL emitters and the promising dual-
stabilizer-capped CdSe NCs.32 ECL of CsPbBr3 NCs|GCE might
be of the highest color purity for all of the reported ECL systems
in an aqueous medium to the best of our knowledge.15
The as-prepared CsPbBr3 NCs displayed a distinct first
electronic absorption peak at 509 nm and a symmetric PL peak at
516 nm with a full width at half-maximum (fwhm) of 19 nm,
which was consistent with previously reported results.15 A PL
decay curve of CsbBr3 NCs was well-fitted with a triexponential
decay model (Table S1), and the PL lifetime was determined to
be of 95.9 ns (inset A). X-ray diffraction (XRD) and transmission
electron microscopy (TEM) patterns proved that CsPbBr3 NCs
were of perfect cubic crystal structure (Figures S1 and S2).15
Scanning electron microscopy (SEM) patterns (insets B and C)
proved that CsPbBr3 NCs were uniformly dispersed on the GCE
surface.15
No obvious electrochemical and ECL responses were detected
with a bare GCE in 0.10 M phosphate buffer (PB) containing 0.0
or 0.10 μM H2O2 (Figure S3) because no obvious charge transfer
occurred on a bare GCE in PB without the presence of CsPbBr3
NCs (curves a and b, inset A of Figure 2). The slightly enhanced
Previous research has demonstrated that the anodic ECL of
CsPbBr3 NCs|GCE in an organic medium could only be achieved
with the presence of tri-n-propylamine,15 while no anodic ECL
was achieved on CsPbBr3 NCs|GCE in the same organic medium
without coreactant.15 The anodic ECL of CsPbBr3 NCs|GCE in a
bare PB might be associated with some electrochemically
generated chemicals (or radicals) at the GCE surface, which
could chemically reduce CsPbBr3 NCs to negatively charged
states (R−) by injecting electrons onto the lowest unoccupied
molecular orbitals (LUMOs). It was previously demonstrated
•−
−
that ROS, such as O2 or HO2 , could be electrochemically
generated at the anode and react with ECL chemicals for anodic
ECL in an aqueous medium.33 Herein, CsPbBr3 NCs|GCE did
demonstrate both an enhanced oxidative current (Figure 2B)
and obviously enhanced ECL with an onset of around +0.8 V and
a maximum emission of around +1.25 V (Figure 2A) by
introducing 0.10 μM H2O2 into the aforementioned bare PB.
The ECL spectrum of CsPbBr3 NCs|GCE in PB containing 0.10
μM H2O2 was also almost the same to the PL spectrum,
indicating that H2O2 participated in the anodic charge transfer
for the anodic ECL of CsPbBr3 NCs without altering the excited
states.
Actually, ECL of CsPbBr3 NCs|GCE in both bare PB and PB
containing 0.10 μM H2O2 displayed similar onset potentials,
while CsPbBr3 NCs|GCE displayed an enhanced DPV response
in PB containing 0.10 μM H2O2 over that in blank PB, indicating
that the electrochemical oxidation of H2O2 on CsPbBr3 NCs|
GCE did produce some radicals of strong reducing ability, which
could reduce CsPbBr3 NCs to negatively charged states (R−) by
injecting electrons onto the LUMOs. The enhanced ECL with
the presence of H2O2 not only confirmed that H2O2 could
participate in the redox and ECL of perovskite CsPbBr3 NCs but
also manifested that CsPbBr3 NCs have the ability to store
charges, which could subsequently lead to ECL upon hole and/
or electron transfer.17 Along with the monochromatic ECL of
CsPbBr3 NCs|GCE in an organic medium,15 ECL of CsPbBr3
NCs|GCE in an aqueous medium further confirmed that
CsPbBr3 NCs|GCE could preserve the highly passivated surface
states of NCs in both organic and aqueous media and bring out
ECL of the same excited states. The mechanism for ECL of
CsPbBr3 NCs|GCE in PB was embodied by eqs 1−6.
Figure 2. (A) ECL and (B) cyclic voltammetry of CsPbBr3 NCs|GCE in
0.10 M pH 7.4 PB containing (a) 0.0 and (b) 0.1 μM H2O2 at 50 mV/s.
Inset: (A) DPV profiles of (a and b) a bare GCE and (c and d) CsPbBr3
NCs|GCE in 0.10 M pH 7.4 PB containing (a and c) 0.0 and (b and d)
0.1 μM H2O2 at 50 mV/s. (B) ECL spectra of CsPbBr3 NCs|GCE in
0.10 M pH 7.4 PB containing (a) 0.0 and (b) 0.1 μM H2O2 at 50 mV/s.
current of a GCE in PB containing H2O2 than the same GCE in
bare PB is probably due the anodic oxidation of H2O2. The
obvious oxidative peak on the differential pulse voltammetry
(DPV) profile of CsPbBr3 NCs|GCE in a bare PB (curve c, inset
A of Figure 2) manifested that CsPbBr3 NCs could be
electrochemically oxidized to positively charged states (R+) by
injecting holes onto highest occupied molecular orbitals
(HOMOs).15,17
Although CsPbBr3 NCs|GCE displayed much lower electro-
chemical response than the GCE in a bare PB (Figures 2B and
S3B), obvious anodic ECL with an onset potential of around +0.8
V and maximum emission of around +1.12 V was also achieved
on CsPbBr3 NCs|GCE in a bare PB without any traditional
coreactant (curve a, Figure 2A). Despite the poor stability of
perovskite NCs in polar solvents,28 herein the anodic ECL might
indicate that CsPbBr3 NCs|GCE is stable enough for the
electrochemical redox and ECL in an aqueous medium.
Importantly, the ECL spectrum displayed a single and symmetric
peak around 518 nm (2.39 eV) with a fwhm of 20 nm. The ECL
−
3OH− − 2e → HO2 + H2O
(1)
or
−
−
H2O2 + OH− → HO2 + H2O → O2
(2)
(3)
(4)
−
O2 + R → R−
R − e → R+
B
DOI: 10.1021/acs.inorgchem.7b01515
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Inorganic Chemistry
Communication
R− + R+ → R*
R* → R + hν
(5)
(6)
even the mixture of these compounds also demonstrated
negligible interference with H2O2 at the 0.1 μM level. The
monochromatic and H2O2-involved ECL might eventually
enable promising applications of perovskite NCs beyond
optoelectronic and photovoltaic devices.4,5
ECL of CsPbBr3 NCs|GCE increased gradually with the
increased concentration of H2O2 in PB (Figure 3). A linear
In conclusion, the charge-transfer-related anodic redox and
ECL of all-inorganic perovskite CsPbBr3 NCs was investigated in
an aqueous medium for the first time. CsPbBr3 NCs could be
electrochemically oxidized to the oxidative states at anodes, while
some ROS could chemically reduce CsPbBr3 NCs to reductive
states. The charge transfer of CsPbBr3 NCs between oxidative
and reductive states could bring out monochromatic ECL in an
aqueous medium, which might present a way to design a ECL
strategy of high color selectivity with highly crystallized NCs. A
small biomolecule, such as H2O2, could selectively enhance the
anodic ECL without changing its spectral features. The
promising redox and ECL nature of CsPbBr3 NCs in an aqueous
medium not only opened the way to design biochemical-involved
optoelectronic and photovoltaic devices but also indicated that
polar solvents could also be used to investigate the redox nature
of CsPbBr3 NCs under given conditions.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b01515.
Figure 3. ECL of CsPbBr3 NCs|GCE in 0.10 M pH 7.4 PB containing
(a) 0.0, (b) 0.020, (c) 0.030, (d) 0.050, (e) 0.10, (f) 0.50, and (g) 1.0 μM
H2O2 at 50 mV/s. Inset: Calibration curve for H2O2 detection.
Experimental section, XRD, TEM, and PL lifetime
characterizations of the CsPbBr3 NCs, and ECL control
testing (PDF)
relationship between the maximum ECL intensity and the
logarithm of the H2O2 concentration was obtained from 0.030 to
1.0 μM (the inset of Figure 3), and the limit of detection was
0.020 μM (S/N = 3). The performance of CsPbBr3 NCs|GCE-
based ECL for determining H2O2 was superior to some
nonenzymatic ECL, amperometric, and colorimetric strategies
(Table S2).34−37
Importantly, the anodic ECL of CsPbBr3 NCs|GCE was highly
selective toward H2O2 (Figure 4). Common interfering
substances for determining H2O2, such as ascorbic acid (AA),
uric acid (UA), dopamine (DA), and glucose, displayed
negligible ECL response on CsPbBr3 NCs|GCE in blank PB;
AUTHOR INFORMATION
Corresponding Authors
*E-mail: zouguizheng@sdu.edu.cn.
*E-mail: hswang@lcu.edu.cn.
ORCID
■
Guizheng Zou: 0000-0002-3295-3848
Bin Zhang: 0000-0002-1529-6356
Author Contributions
§Y.H. and X.L. contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This project was supported by the National Natural Science
Foundation of China (Grants 21427808, 21375077, and
21375055) and the Fundamental Research Foundation of
Shandong University (Grant 2015JC037).
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