Research Article
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A Full-Spectrum Porphyrin–Fullerene D–A Supramolecular
Photocatalyst with Giant Built-In Electric Field for Efficient
Hydrogen Production
Jun Yang, Jianfang Jing, and Yongfa Zhu*
A full-spectrum (300–850 nm) responsive donor–acceptor (D–A) supramo-
lecular photocatalyst tetraphenylporphinesulfonate/fullerene (TPPS/C60) is
successfully constructed. The theoretical spectral efficiency of TPPS/C60 is as
high as 70%, offering the possibility of full-solar-spectrum light harvesting.
The TPPS/C60 performs a highly efficient photocatalytic H2 evolution rate
of 276.55 µmol h−1 (34.57 mmol g−1 h−1), surpassing many reported organic
photocatalysts. The D–A structure effectively promotes electron transfer from
TPPS to C60, which is beneficial to the photocatalytic reaction. Specifically,
a giant internal electric field in the D–A structure is built via the enhanced
molecular dipole, which dramatically promotes the charge separation (CS)
efficiency by 2.35 times. Transient absorption spectra results show a long-
lived CS state TPPS•+–C60•− in the D–A structure, which effectively promotes
participation of photogenerated electrons in the reduction reaction. Briefly,
this work provides a novel approach for designing high-performance photo-
catalytic materials via enhancing the interfacial electric field.
1. Introduction
Photocatalytic solar energy transformation is a very helpful
way to solve global energy demand.[1] So far, great efforts have
been made to explore highly efficient photocatalytic materials
for hydrogen production, but the photocatalytic efficiency
is still unsatisfactory and far away from the potential actual
requirements.[2] One of the significant factors is the limited
solar spectral response range for most materials. As we all
know, the solar spectrum is composed of 5% ultraviolet light,
42–45% visible light, and more than 50% near-infrared (NIR)
light. However, developing materials that can capture as much
of the solar spectrum as possible is still a daunting challenge.[3]
In addition to light harvesting, the energy band structure and
charge separation (CS) efficiency are the other two critical fac-
tors determining photocatalytic activity.[4] Particularly, the redox
capacity is thermodynamically determined by the position of
the edges of the conduction band (CB) and valence band (VB)
Dr. J. Yang, Dr. J. Jing, Prof. Y. Zhu
Department of Chemistry
Tsinghua University
Beijing 100084, P. R. China
E-mail: zhuyf@tsinghua.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202101026.
DOI: 10.1002/adma.202101026
Adv. Mater. 2021, 33, 2101026 2101026  (1 of 8)
of the material.[5] Besides, charge carriers
need to transfer through the bulk to the
surface of the material in order to reach
the active site of redox reactions. However,
the holes and electrons recombine easily
as they migrate in the bulk phase. In this
process, the best way to maximize cata-
lytic activity is to increase the separation
efficiency of photogenerated carriers and
prevent electron consumption during bulk
and surface transport.[6]
Recently, a series of promising self-
assembled supramolecular materials were
developed by our group and applied to
photocatalytic hydrogen and oxygen pro-
duction.[7] Especially porphyrin, due to its
excellent photoelectric conversion perfor-
mance, has aroused our interest in recent
years. A large number of modified deriva-
tives can be obtained from the porphyrin
ring, which has good light-harvesting
ability in the entire natural spectrum.[8] However, porphyrin-
based materials exhibit very limited hydrogen production per-
formance as photocatalysts, which is mainly affected by the low
separation efficiency of photogenerated carriers. Numerous
studies have proved that the internal electric field is the main
kinetic factor for photogenerated CS.[9] It has been proved that
changing the functional group can control the dipole and the
frontier orbital energy level of the molecule, thereby regulating
the built-in electric field and energy band of photocatalysts.
However, it produces little effect on the photocatalytic activity.[10]
Therefore, it is particularly important to find efficient methods
to improve the photocatalytic performance.
In view of the key scientific issues above, a full-spectrum
(300–850  nm) responsive metal-free TPPS/C60 supramolecular
photocatalyst with electronic donor–acceptor (D–A) characteristic
is successfully constructed via strong electrostatic interaction and
π–π action. This is inspired by: i) Porphyrin molecule has rela-
tively large dipole for the construction of the built in electric field
and its high molar absorption coefficient is helpful for light-har-
vesting. More than that, porphyrin has unique electron-donating
properties.[11] ii) The π-electron system of C60 is highly delocal-
ized on its 3D curved surface, which makes small recombina-
tion energy during the electron transfer process. Therefore, C60
can be used as the electron acceptor.[12] iii) The molecular dipole
may increase by constructing a D–A system via strong electro-
static interaction, thereby enhancing the built-in electric field and
increasing the driving force for photogenerated carrier separation.
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Figure 1.  a) The frontier molecular orbital distribution of TPPS/C60-NH2. b) The ESP of TPPS/C60-NH2. c) UV–vis absorption spectroscopy of samples.
d) HRTEM image of TPPS/C60-NH2.
2. Results
2.1. The D–A Supramolecular Structure of TPPS/C60
First, the TPPS/C60 sample was successfully prepared via
electrostatic interaction and π–π interaction, as shown in the
supporting information (Figure S2, Supporting Information).
The results of frontier molecular orbital distribution were
calculated by DFT, b3lyp, 6–311G (Figure S3, Table S1, Sup-
porting Information). Theoretical calculations show that the
HOMO and LUMO of TPPS/C60 are located on the porphyrin
moiety and C60 moiety respectively (Figure  1a), which con-
forms to the characteristics of D–A structure.[13] The structure
benefits spatial CS. Besides, electrochemical test was used
to check the HOMO and LUMO of the catalyst (Figures S4,
S5, Supporting Information), which matched well with the
computing results. As shown in Figure  1b and Figure S6,
Supporting Information, the electrostatic potential distribu-
tion (ESP) shows that TPPS and C60 are tightly combined
through electrostatic interaction between the sulfonic acid
group and the protonated amino group. Experimentally, the
electrostatic interaction between TPPS and C60 is also proved
by ultraviolet absorption and fluorescence emission spectra,
as shown in Figure S7, Supporting Information. Furthermore,
the aggregation behavior of TPPS was investigated by its
favorable spectroscopic characteristics. As shown in Figure 1c,
the UV–vis spectra show that the typical Soret band and Q
bands of porphyrin. Simultaneously, the Soret band of TPPS/
C60 exhibited a redshift and the number of Q-bands reduced
compared with the TPPS monomer, indicating the J-type
accumulation is formed.[14] In addition, the steady-state fluo-
rescence spectrum further ensures the J-type π–π stacking,
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as shown in Figure S9, Supporting Information. Compared
with H-type aggregation, TPPS self-assembly generally shows
a J-type aggregation with lower stacking Gibbs energy. It is
interesting to note that the J-type accumulation can better
imitate the chlorophyll in photosynthesis in nature.[15] Simul-
taneously, the X-ray diffraction spectrum (XRD) as shown
in Figure S10, Supporting Information, also indicates short-
range π–π stacking aggregation. Short-range accumulation
can not only weaken the strong aggregation effect between
TPPS molecules, thereby enhancing electron diffusion and
dissociation, but also promote its photon absorption and CS.
On the contrary, long-range accumulation results in greater
energy loss due to the longer electron transfer distance, which
is more likely to cause thermal relaxation and quenching.[16]
Besides, as shown in Figure S11, Supporting Information, the
IR spectra provide detailed functional group information of
samples. And owing to the aggregation, the molecular iso-
lated energy level of the monomer TPPS is liner combined
into semiconductor energy band in self-assembled TPPS
(Figure S12, Supporting Information).
The information of morphology and highly crystalline struc-
ture of samples are shown in Figures S13–S16, Supporting
Information. It is observed that TPPS/C60 exhibits high crystal-
linity as shown in Figure  1d. Obviously, d-spacing of 0.7 and
1.5  nm can be observed vertically, corresponding to the diam-
eters of C60 and TPPS molecule, respectively.[17] Simultane-
ously, the d-spacing 0.313 nm is belonging to the π–π stacking
spacing. The structural advantage of high crystallinity makes
TPPS/C60 have a strong built-in electric field, which makes it
have good CS and transfer capabilities.[7a,18] Accordingly, the
prominent photocatalytic activity of the D–A catalyst TPPS/C60
is also expected.
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Figure 2.  a) The photocatalytic hydrogen evolution of TPPS/C60-NH2 with time under full-spectrum (674.33  mW cm−2). b) The comparison of H2
evolution rate under full-spectrum light. c) Overlayer of wavelength-dependent hydrogen evolution and UV–vis absorption. d) Overlayer of AQE and
UV–vis absorption.
2.2. The Highly Efficient Photocatalytic Activity by Construction
of D–A Material
The photocatalytic hydrogen production test was performed
under full-spectrum and ascorbic acid was used as a sacrificial
agent. More detailed information about photocatalytic proper-
ties can be found in Figures S17–S26, Supporting Information.
TPPS/C60 showed greatly efficient hydrogen production, which
achieved 276.55 µmol h−1 (34.57 mmol g−1 h−1) under full-spec-
trum light (Figure  2a). The catalytic activity of TPPS/C60 was
6.03 times that of TPPS, as exhibited in Figure  2b. Simulta-
neously, the TPPS/C60 exhibited more excellent photocatalytic
activity in comparison with the typical graphitic carbon nitride
(C3N4). As shown in Table S2, Supporting Information, com-
pared with recently reported porphyrin-based materials, TPPS/
C60 is one of the top catalysts in terms of hydrogen produc-
tion performance among these materials. Furthermore, the
wavelength-dependent photocatalytic activities and the apparent
quantum yield (AQY) were investigated as shown in Figure 2c
and Figure  2d. The results show that the hydrogen evolution
rate and the apparent quantum efficiency (AQE) are both
positively related to the absorption spectrum. The optimum
hydrogen evolution rate reached up to 452.56  µmol g−1 h−1 at
650 nm and the maximum AQE also appears at 650 nm. While,
it needs to be emphasized that in the currently reported pho-
tocatalytic hydrogen generation materials, few photocatalysts
have such a broad response to wavelength, covering from ultra-
violet to visible to red light. Even for the star material C3N4, the
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main hydrogen production wavelength is concentrated around
420  nm, and there is almost no hydrogen production activity
under ultraviolet and red light. However, TPPS/C60, achieves
a wide spectral photocatalytic response, which is important
for making the most of sunlight. This D–A structure catalyst
TPPS/C60 provides the possibility to broaden the full use of the
solar spectrum.
In view of such excellent activity, it is particularly necessary
to investigate thoroughly the pivotal scientific factors affecting
the catalytic properties of the D–A material.
2.3. The Thermodynamic Factors for Highly Efficient Charge
Separation of TPPS/C60
On the one hand, the thermodynamic factors are studied. First,
according to the research of Domen and Wang, the first step
of photocatalysis is photon absorption.[19] Enlarging the light
absorption of the material can greatly improve the ideal solar
energy conversion efficiency. Therefore, in order to obtain
higher solar energy conversion efficiency, it is essential to
develop photocatalysts that can capture light strongly.[20] As
shown in Figure 3a, the theoretical spectral efficiency of TPPS/
C60 is as high as 70%, covering the whole solar spectrum. The
intrinsic absorption band edge of TPPS/C60 even reaches the
infrared region 843 nm. Second, the feasibility of the photocata-
lytic reduction reaction is closely related to the position of the
energy band. According to the electrochemical Mott–Schottky
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Figure 3.  a) The UV–vis diffuse reflection spectroscopy of TPPS/C60-NH2 power, and solar spectrum observed using an optical fiber spectrometer.
b) Schematic drawing of redox potentials of samples. c) Frontier molecular orbital distribution in the TPPS/C60-NH2. d) EIS Nyquist plots of TPPS and
TPPS/C60-NH2 powder. e) Room-temperature PL emission spectra of TPPS, TPPS/C60-NH2, and TPPS-unfunctional. f) Transient fluorescence lifetime
of TPPS, TPPS/C60-NH2, and TPPS-unfunctional.

plots (Figure S27, Supporting Information), the positive slopes
demonstrate the n-type semiconductor characteristics of TPPS
and TPPS/C60. In general, for an n-type semiconductor, the flat-
band potential is approximately at the CB potential.[9c] Thus,
the CB potential of −1.41  V versus NHE (pH = 7) for TPPS/
C60 can be obtained, which is much lower than individual
TPPS (Figure 3b). Consequently, TPPS/C60 can more effectively
reduce water into hydrogen. Thirdly, according to the com-
puting results as shown in Figure 3c, the HOMO and LUMO of
TPPS/C60 are located on the porphyrin moiety and C60 moiety
respectively, which conforms to the characteristics of D–A
structure. It should be pointed out that the LUMO and HOMO
would be linearly recombined to form a semiconductor energy
band after π–π interaction.[21] The π–π stacking is conducive to
expanding conjugated electron clouds, resulting in the intrinsic
absorption edge of TPPS/C60 even reaches the infrared region.
Simultaneously, the first unoccupied orbital belonging to the
porphyrin is found at LUMO+4 as shown in Figure  3c, which
means that there are consequently four unoccupied orbitals
that can facilitate the transfer of electrons from the excited state
of the porphyrin to the fullerene, which is beneficial to the pho-
tocatalytic process.[22]
The behavior of photoinduced charge was further explored
experimentally. The electrochemical impedance spectroscopy
(EIS) was first carried out (Figure  3d). The diameter of arc
can reflect the charge-transfer resistance.[23] Obviously, the arc
radius of TPPS/C60 is much smaller than the pure TPPS, sug-
gesting the D–A structure is conducive to decreasing the charge
transfer resistance. The decreased charge transfer resistance is
very helpful for charge transfer.
Besides, the fluorescence emission can be formed by the
recombination of h+–e− pairs. Generally speaking, CS effi-
ciency can be reflected by fluorescence intensity.[24] As shown in
Figure 3e, an obvious fluorescence signal at 676 nm was found
for pure TPPS. The fluorescence emission intensity of TPPS/
C60-unfunctional decreased slightly, while the emission peak of
TPPS/C60-NH2 significantly decreases. Under the strong π–π
action, photogenerated carriers are generated as a non-radia-
tive transition on account of aggregation-induced fluorescence
quenching.[25] Specifically speaking, since there is no strong
electrostatic interaction between TPPS and C60-unfunctional,
it is difficult to form an effective D–A structure, which is not
conducive to the separation of carriers. However, there is a
strong electrostatic interaction between TPPS and C60-NH2 for
ionic self-assembly to form an effective D–A structure, which
can facilitate photoinduced electron transfer from the excited
singlet state of the porphyrin to the C60 moiety and the built-in
electric field redistributes the charge density.
As shown in Figure  3f, it was found that the time-resolved
fluorescence of TPPS followed a mono-exponential decay with
a lifetime of 4.079  ns (= (τF)ref ). The addition of C60-NH2 and
C60-unfunctional accelerated the fluorescence decay of TPPS.
Obviously, C60-NH2 accelerated decay much faster than the
C60-unfunctional, in accordance with the trend of steady-state
fluorescence quenching in Figure 3e. The fluorescence attenu-
ation curves of TPPS/C60-NH2 and TPPS/C60-unfunctional
both conform to the bi-exponential decay function. The shorter
components ((τF)nanohybrid) are evaluated as 1.608  ns (fraction
(Fr) = 92.23%) for C60-NH2 and 3.573  ns (Fr = 54.96%) for
C60-unfunctional, suggesting the occurrence of intramolecular

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Figure 4.  a) Surface potential of TPPS and TPPS/C60 detected with KPFM. b) The ESP and molecular dipole of TPPS, C60-NH2, and TPPS/C60-NH2. The
results were calculated by DFT, b3lyp, 6–311g. c) Transient absorption spectra of TPPS/C60-NH2 at different time delays after nanosecond laser excita-
tion at 436 nm (1 × 10−5 m, aqueous solution). d) Transient absorption spectra of TPPS/C60-NH2 and TPPS at 8 ps after femtosecond laser excitation
at 400 nm (1 × 10−5 m, aqueous solution). e) Transient absorption decay kinetics of TPPS and TPPS/C60-NH2 at 505 and 716 nm.

electron-transfer from the singlet excited TPPS to the fullerene
entity.[26] And the remaining longer components are attributed
to the non-interacting porphyrin entities. Obviously, the propor-
tion of longer components of TPPS/C60-NH2 (7.77%) is much
smaller than that of TPPS/C60-unfunctional (45.06%), indi-
cating that most of the TPPS in TPPS/C60-NH2 interact with
C60-NH2. These fast decaying components serve as additional
evidence for the formation of TPPS/C60-NH2 nanohybrid. In
particular, it is obvious that the (τF)nanohybrid of TPPS/C60-NH2
is much shorter than TPPS/C60-unfunctional. According to the
literature, the shortening of the fluorescence lifetimes can be
ascribed to the CS process.[27] The rate constants of CS (kCS)
were evaluated in a usual manner from the shorter τ values
assuming that all the quenching was due to the CS from
the singlet excited state of TPPS.[26] The rate constants of CS
(kCS) were determined from the following equation using the
fluorescence lifetimes: kcs = [1/τ(sample)] − [1/(τF)ref ].[27] There-
fore, it can be obtained that the CS rate of TPPS/C60-NH2 is
3.767  × 108 s−1, which is 10.85 times that of TPPS/C60-unfunc-
tional (3.472  × 107 s−1). Such a high CS rate of TPPS/C60-NH2
contributes to the excellent photocatalytic performance.
2.4. The Kinetic Factors for Highly Efficient Charge Separation
of TPPS/C60
On the other hand, the built-in electric field is a primary
kinetic factor affecting CS.[7a] According to Zhang’s group,
the built-in electric field is positively correlated with the zeta
potential and surface potential for a given material.[6,9a] As
shown in Figure  4a, the surface potential can be obtained by
atomic force microscopy with a Kelvin probe. Obviously, the
surface potential of TPPS/C60 (ΔE = 66.83 mV) is significantly
higher than that of TPPS (ΔE = 12.91 mV). Besides, as shown
in Table S5, Supporting Information, the absolute value of
the zeta potential of TPPS/C60 (−62.68  mV) is also enlarged
obviously than the individual TPPS (−44.14  mV). Besides, the
molecular dipole of materials is an important factor affecting
the internal electric field. As shown in Figure  4b, the dipole
of TPPS/C60 is 12.37 Debye, which is much larger than that
of TPPS (3.94 Debye). The larger molecular dipole of the D–A
system ensures a large enough built-in electric field, which
benefits the photoinduced carrier separation. As a result, the
stronger built-in electric field of D–A catalyst TPPS/C60 sig-
nificantly enhanced the CS and transportation. Furthermore,
according to the reported literature by Kanata et  al.,[28] it
can be obtained the internal electric field intensity of TPPS/
C60 is 2.77 times as high as that of TPPS. The relevant evi-
dence is provided in the Supporting Information, such as the
increased surface photovoltage intensity (Figure S28, Sup-
porting Information) and the enhanced surface charge density
(Figure S29, Supporting Information). The enhanced built-in
electric field contributes to higher CS efficiency in the surface
of TPPS/C60 (ηsurface  = 81.62%), which is much higher than
TPPS (ηsurface  = 34.71%), as shown in Figure S30, Supporting
Information.
Furthermore, the electron transport and charge-separated
state were investigated via transient absorption spectra. First,
the signals in the visible region were explored by nanosecond
transient absorption. As illustrated in Figure  4c, TPPS/C60-NH2

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has an obvious negative bleaching peak near the wavelength of
645  nm, and two positive excitation absorption bands near 505
and 716  nm. The bleaching peak near 645  nm is located near
the Q-band (S0→ S1). The transient absorption band between
450 and 610 nm coincides with the B band (Soret band) of TPPS
(S0→ S2), indicating the formation of S2 singlet state, namely
TPPS•+ (S2). The absorption at near 716  nm is located in the Q
band (S0→ S1), which belongs to the absorption of S1 singlet
state, namely, 1TPPS* (S1). As for TPPS, the nanosecond tran-
sient absorption is shown in Figure S31, Supporting Information,
the transient absorption signal intensity of TPPS is much weaker
than that of TPPS/C60 under the same delay time. More than
that, the characteristic peak positions of TPPS/C60-NH2 are red-
shifted compared with TPPS. Besides, the signals in the infrared
region were further detected by femtosecond transient absorp-
tion. As shown in Figure 4d and Figure S32, Supporting Informa-
tion, obvious C60•− signal was detected for TPPS/C60, indicating
that electron transfer from the singlet excited state 1TPPS* to C60,
resulting in the charge-separated state, namely TPPS•+–C60•−.[29]
What’s more, the lifetime of the charge-separated state plays
a vital role in the photocatalytic reaction.[30] In order to study the
relaxation dynamics of TPPS and TPPS/C60 under light excita-
tion, the transient decay dynamics were analyzed throughout
the transient spectrum region. As shown in Figure  4e, the fit-
ting results are all in line with the first-order exponential attenu-
ation. The lifetime of the charge transfer state of TPPS/C60-NH2
at 505  nm and 716  nm are all longer than that of TPPS. The
transient absorption decay fitting results of TPPS/C60-NH2 are
shown in Figure S33, Supporting Information. The lifetime of
charge-separated states reaches 3.16 (λ  = 505  nm) and 3.24 µs
(λ = 716 nm), indicating that there is an efficient electron transfer
process from TPPS to C60. Besides, the transient absorption
Figure 5.  Schematic mechanism of the D–A supramolecular photocatalyst.
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of TPPS/C60-unfunctional has been explored. As shown in
Figure S34A, Supporting Information, the characteristic absorp-
tion peaks of TPPS/C60-unfunctional are similar to those of
TPPS and TPPS/C60-NH2. As shown in Figure S34B, Supporting
Information, the transient decay dynamics were analyzed at
501  nm. The fitting result conformed to the mono-exponential
decay function. The lifetime of the charge transfer state of TPPS/
C60-unfunctional at 501 nm was 2.19 µs, which is larger than that
of TPPS (1.19 µs), but smaller than that of TPPS/C60-NH2 (3.16
µs). This trend is consistent with their hydrogen production per-
formance trend, indicating that the long-lived charge transfer
state helps to improve the photocatalytic performance.
2.5. The Photocatalytic Mechanism of the D–A Supramolecular
TPPS/C60
Based on the above, the photocatalytic mechanism of the D–A
material is presented in Figure 5. To summarize briefly, TPPS
and C60-NH2 are combined through strong electrostatic inter-
action and π–π action. The highest occupied molecular orbital
is located on the porphyrin, whereas the lowest unoccupied
molecular orbital is on the fullerene, which accords with the
typical characteristic of D–A structure. TPPS performs short-
range self-assembly via edge-to-edge J-type π–π stacking. Under
π–π stacking, the overlap of LUMO and HOMO constitutes the
energy bands (CB and VB), which builds the charge transfer
channels. Under light, TPPS/C60 is excited. Then the robust
built-in electric field facilitates the photogenerated electrons
transfer from TPPS to the electron acceptor C60, forming a
long-lived CS intermediate state, namely TPPS•+–C60•−. The
long-lived charge-separated state promotes photogenerated
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electrons to participate in the reduction reaction with the help
of Pt as the co-catalyst and ascorbic acid as the sacrificial agent,
and hydrogen can be quickly produced.
3. Conclusion
A full-spectrum (300–850 nm) D–A supramolecular photocata-
lyst TPPS/C60-NH2 was successfully constructed. A giant built-
in electric field was formed via regulating molecular dipoles,
which was conducive to dramatically accelerating CS. Conse-
quently, a long-lived charge-separated state was formed, and
a highly efficient hydrogen production performance was real-
ized, which was higher than many reported supramolecular-
based materials. Briefly, this work provides a novel approach
for designing high-performance photocatalytic materials via
enhancing the interfacial electric field for the use of hydrogen
production, which is expected to contribute to clean energy
production.
4. Experimental Section
All the chemicals were purchased from Sigma-Aldrich and used without
further purification.
Synthesis of C60-NH2: The preparation of C60-NH2 referred to the
reported literature.[31] It was prepared by a simple solid–liquid reaction.
Specifically, commercial fullerene (20 mg) was added to a round-bottom
flask containing ethylenediamine (100  mL), the mixture was stirred
at 50  °C for 24 h, and then sonicated for 5 h until the fullerene was
completely dissolved in ethylenediamine. Then, the ethylenediamine was
removed by a rotary evaporator, and the remaining solid was dissolved
in an aqueous solution of HCl (1 mol L−1) for use. The concentration of
C60-NH2 was controlled at 0.2 mg mL−1.
Preparation of Self-Assembled TPPS and TPPS/C60-NH2: First, the
commercial TPPS (0.1mmol, 0.0934 g) was dissolved in deionized water
(50  mL), then triethylamine (200  µL) was added to it, the solution
turned into a dark red transparent liquid. Then the pH was adjusted to 2
with dilute hydrochloric acid, and stirred at 50 °C for 1 h. Then the above
acid solution of C60-NH2 with different volumes was added to it under
stirring and high-power ultrasound for 2 h. Finally, 0.22 micron filter
membrane was used for suction filtration and the dark green solid would
be collected, which was dried at 60  °C, namely TPPS/C60 (TPPS/C60-X,
“X” represents the feeding mass fraction of C60-NH2 relative to TPPS,
namely 1, 3, 4, 5, 6, 7, 9, 10, and 15%). The schematic diagram of material
preparation is shown in Figure S2, Supporting Information. It should be
pointed out that TPPS/C60-5% was selected for the data characterization
in this paper, which performed the best catalytic performance.
Self-assembled TPPS was prepared in the absence of C60-NH2.
Besides, the C3N4 as a contrast sample was prepared according to
the reported reference.[32]
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was partly supported by Chinese National Science Foundation
(21872077, 21621003) and National Key Research and Development
Project of China (2020YFA0710304).
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Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Keywords
charge separation, donor–acceptor systems, hydrogen production,
photocatalysis, TPPS/C60
Received: February 5, 2021
Revised: April 1, 2021
Published online: July 8, 2021
[1] a) C.  Xu, P. R.  Anusuyadevi, C.  Aymonier, R.  Luque, S.  Marre,
Chem. Soc. Rev. 2019, 48, 3868; b) T. Banerjee, F. Podjaski, J. Kröger,
B. P. Biswal, B. V. Lotsch, Nat. Rev. Mater. 2021, 6, 168.
[2] a) X. Meng, L. Liu, S. Ouyang, H. Xu, D. Wang, N. Zhao, J. Ye, Adv.
Mater. 2016, 28, 6781; b) J. D.  Xiao, H. L.  Jiang, Acc. Chem. Res.
2019, 52, 356.
[3] D. Li, S. H. Yu, H. L. Jiang, Adv. Mater. 2018, 30, 1707377.
[4] C. E. Nebel, Nat. Mater. 2013, 12, 780.
[5] a) J.  Kou, C.  Lu, J.  Wang, Y.  Chen, Z.  Xu, R. S.  Varma, Chem. Rev.
2017, 117, 1445; b) Y. Liu, S. Ye, H. Xie, J. Zhu, Q. Shi, N. Ta, R. Chen,
Y.  Gao, H.  An, W.  Nie, H.  Jing, F.  Fan, C.  Li, Adv. Mater. 2020, 32,
1906513.
[6] J.  Li, L.  Cai, J.  Shang, Y.  Yu, L.  Zhang, Adv. Mater. 2016, 28,
4059.
[7] a) Z. Zhang, X. Chen, H. Zhang, W. Liu, W. Zhu, Y. Zhu, Adv. Mater.
2020, 32, 1907746; b) D. Liu, J. Wang, X. Bai, R. Zong, Y. Zhu, Adv.
Mater. 2016, 28, 7284.
[8] a) A. Wang, J. Ye, M. G. Humphrey, C. Zhang, Adv. Mater. 2018, 30,
1705704; b) K. Gao, Y. Kan, X. Chen, F. Liu, B. Kan, L. Nian, X. Wan,
Y. Chen, X. Peng, T. P. Russell, Y. Cao, A. K. Y. Jen, Adv. Mater. 2020,
32, 1906129; c) J. Choi, P. Wagner, R. Jalili, J. Kim, D. R. MacFarlane,
G. G.  Wallace, D. L.  Officer, Adv. Energy Mater. 2018, 8, 1801280;
d) J.-Y.  Shin, K. S.  Kim, M.-C.  Yoon, J. M.  Lim, Z. S.  Yoon,
A.  Osuka, D.  Kim, Chem. Soc. Rev. 2010, 39, 2751; e) C.  Zhang,
P.  Chen, H.  Dong, Y.  Zhen, M.  Liu, W.  Hu, Adv. Mater. 2015, 27,
5379.
[9] a) J.  Li, G.  Zhan, Y.  Yu, L.  Zhang, Nat. Commun. 2016, 7, 11480;
b) Y.  Guo, W.  Shi, Y.  Zhu, EcoMat 2019, 1, e12007; c) X.  Chen,
J.  Wang, Y.  Chai, Z.  Zhang, Y.  Zhu, Adv. Mater. 2021, 33, 2007479;
d) Y.  Wu, H.  Wang, Y.  Sun, T.  Xiao, W.  Tu, X.  Yuan, G.  Zeng,
S.  Li, J. W.  Chew, Appl. Catal., B 2018, 227, 530; e) Y.  Lin, C.  Yang,
S.  Wu, X.  Li, Y.  Chen, W. L.  Yang, Adv. Funct. Mater. 2020, 30,
2002918.
[10] Z. Zhang, Y. Zhu, X. Chen, H. Zhang, J. Wang, Adv. Mater. 2019, 31,
1806626.
[11] a) F.  Würthner, T. E.  Kaiser, C. R.  Saha-Möller, Angew. Chem.,
Int. Ed. 2011, 50, 3376; b) F. J. M.  Hoeben, P.  Jonkheijm,
E. W.  Meijer, A. P. H. J.  Schenning, Chem. Rev. 2005, 105, 1491;
c) C. M.  Drain, A.  Varotto, I.  Radivojevic, Chem. Rev. 2009, 109,
1630; d) J. A. A. W.  Elemans, R.  van Hameren, R. J. M.  Nolte,
A. E. Rowan, Adv. Mater. 2006, 18, 1251; e) H. Liu, J. Xu, Y. Li, Y. Li,
Acc. Chem. Res. 2010, 43, 1496.
© 2021 Wiley-VCH GmbH
www.advancedsciencenews.com
[12] a) B.  Park, S. E.  Cho, Y.  Kim, W. J.  Lee, N.-H.  You, I.  In,
E.  Reichmanis, Adv. Mater. 2013, 25, 6453; b) A. M.  Nardes,
A. J.  Ferguson, J. B.  Whitaker, B. W.  Larson, R. E.  Larsen,
K. Maturová, P. A. Graf, O. V. Boltalina, S. H. Strauss, N. Kopidakis,
Adv. Funct. Mater. 2012, 22, 4115; c) R.  Pandey, R. J.  Holmes, Adv.
Mater. 2010, 22, 5301.
[13] a) K.  Wang, C.-J.  Zheng, W.  Liu, K.  Liang, Y.-Z.  Shi, S.-L.  Tao,
C.-S.  Lee, X.-M.  Ou, X.-H.  Zhang, Adv. Mater. 2017, 29, 1701476;
b) M. Wolf, J. I. T. Costa, M. B. Minameyer, T. Drewello, A. C. Tomé,
D. M. Guldi, J. Phys. Chem. C 2019, 123, 28093.
[14] a) L. Zhao, R. Ma, J. Li, Y. Li, Y. An, L. Shi, Biomacromolecules 2008,
9, 2601; b) J. Li, K. Ueno, H. Uehara, J. Guo, T. Oshikiri, H. Misawa,
J. Phys. Chem. Lett. 2016, 7, 2786; c) K. L.  Gurunatha, E.  Dujardin,
J. Phys. Chem. C 2013, 117, 3489.
[15] R. Bera, S. Chakraborty, S. K. Nayak, B. Jana, A. Patra, J. Phys. Chem.
C 2019, 123, 15815.
[16] W. Wei, D. Liu, Z. Wei, Yongfa Zhu, ACS Catal. 2017, 7, 652.
[17] a) M.  Scheer, A.  Schindler, R.  Merkle, B. P.  Johnson, M.  Linseis,
R.  Winter, C. E.  Anson, A. V.  Virovets, J. Am. Chem. Soc. 2007,
129, 13386; b) E.  Káfuňková, C.  Taviot-Guého, P.  Bezdička,
M.  Klementová, P.  Kovář, P.  Kubát, J.  Mosinger, M.  Pospíšil,
K. Lang, Chem. Mater. 2010, 22, 2481.
[18] K. S.  Park, K. S.  Lee, J.  Baek, L.  Lee, B. H.  Son, Y.-E.  Koo Lee,
Y. H. Ahn, W. I. Park, Y. Kang, M. M. Sung, Angew. Chem., Int. Ed.
2016, 55, 10273.
[19] Q. Wang, K. Domen, Chem. Rev. 2020, 120, 919.
[20] a) X.  Wang, F.  Wang, Y.  Sang, H.  Liu, Adv. Energy Mater. 2017, 7,
1700473; b) X.  Xu, F.  Luo, W.  Tang, J.  Hu, H.  Zeng, Y.  Zhou, Adv.
Funct. Mater. 2018, 28, 1804055.
[21] G. Saito, Y. Yoshida, Bull. Chem. Soc. Jpn. 2007, 80, 1.
Adv. Mater. 2021, 33, 2101026 2101026  (8 of 8)
www.advmat.de
[22] H.  Tian, J.  Oscarsson, E.  Gabrielsson, S.  Eriksson, R.  Lindblad,
B.  Xu, Y.  Hao, G.  Boschloo, E.  Johansson, J.  Gardner, A.  Hagfeldt,
H. Rensmo, L. Sun, Sci. Rep. 2014, 4, 4282.
[23] G.  Wang, Q.  Sun, Y.  Liu, B.  Huang, Y.  Dai, X.  Zhang, X.  Qin,
Chem. - Eur. J. 2015, 21, 2364.
[24] S. Usai, S. Obregón, A. I. Becerro, G. Colón, J. Phys. Chem. C 2013,
117, 24479.
[25] N. C. Maiti, S. Mazumdar, N. Periasamy, J. Phys. Chem. B 1998, 102,
1528.
[26] F.  D’Souza, G. R.  Deviprasad, M. E.  Zandler, M. E.  El-Khouly,
M. Fujitsuka, O. Ito, J. Phys. Chem. B 2002, 106, 4952.
[27] S. K.  Das, N. K.  Subbaiyan, F.  D’Souza, A. S. D.  Sandanayaka,
T. Hasobe, O. Ito, Energy Environ. Sci. 2011, 4, 707.
[28] a) T.  Kanata-Kito, M.  Matsunaga, H.  Takakura, Y.  Hamakawa,
T. Nishino, Proc. SPIE 1990, 1286, 56; b) J. S. Im, H. Kollmer, J. Off,
A.  Sohmer, F.  Scholz, A.  Hangleiter, Phys. Rev. B 1998, 57, R9435;
c) P.  Lefebvre, J.  Allègre, B.  Gil, H.  Mathieu, N.  Grandjean,
M.  Leroux, J.  Massies, P.  Bigenwald, Phys. Rev. B 1999, 59, 15363;
d) G.  Morello, F. Della  Sala, L.  Carbone, L.  Manna, G.  Maruccio,
R. Cingolani, M. De Giorgi, Phys. Rev. B 2008, 78, 195313.
[29] K.  Ohkubo, H.  Kotani, J.  Shao, Z.  Ou, K. M.  Kadish, G.  Li,
R. K. Pandey, M. Fujitsuka, O. Ito, H. Imahori, S. Fukuzumi, Angew.
Chem., Int. Ed. 2004, 116, 871.
[30] a) S. Fukuzumi, K. Ohkubo, Dalton Trans. 2013, 42, 15846; b) Y. Hou,
X.  Zhang, K.  Chen, D.  Liu, Z.  Wang, Q.  Liu, J.  Zhao, A.  Barbon,
J. Mater. Chem. C 2019, 7, 12048.
[31] J.  Li, F.  Zhao, T.  Wang, M.  Nie, J.  Li, Z.  Wei, L.  Jiang, C.  Wang,
J. Mater. Chem. A 2017, 5, 947.
[32] X.  Chen, R.  Shi, Q.  Chen, Z.  Zhang, W.  Jiang, Y.  Zhu, T.  Zhang,
Nano Energy 2019, 59, 644.
© 2021 Wiley-VCH GmbH