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Water Splitting www.advenergymat.de

Metal-Free 2D/2D Heterojunction of Graphitic Carbon

Nitride/Graphdiyne for Improving the Hole Mobility
of Graphitic Carbon Nitride
Ying-Ying Han, Xiu-Li Lu,* Shang-Feng Tang, Xue-Peng Yin, Zhen-Wei Wei,
and Tong-Bu Lu*

high physicochemical stability.[9–13] How-

The design and synthesis of efficient metal-free photoelectrocatalysts for ever, using pure g-C3N4 as a photocatalyst
water splitting are of great significance, as nonmetal elements are generally for photocatalytic production of hydrogen
earth abundant and environment friendly. As a typical metal-free semicon- still remains a great challenge. This is
mainly due to the high recombination
ductor, g-C3N4 has received much attention in the field of photocatalytic
rate of photocarriers during their transfer
water splitting. However, the poor photoinduced hole mobility of g-C3N4 process to the surface before participating
restrains its catalytic performance. Herein, for the first time, graphdiyne in the surface redox.[14,15] To this end, it
(GDY) is used to interact with g-C3N4 to construct a metal-free 2D/2D is imperative to facilitate the separation
heterojunction of g-C3N4/GDY as an efficient photoelectrocatalyst for water efficiency of photocarriers to enhance the
photocatalytic activity of g-C3N4.
splitting. The g-C3N4/GDY photocathode exhibits enhanced photocarriers
Up to now, researchers have made great
separation due to excellent hole transfer nature of graphdiyne and the struc- efforts for improving the photocarriers
ture of 2D/2D heterojunction of g-C3N4/GDY, realizing a sevenfold increase in separation of g-C3N4 through modulating
electron life time (610 μs) compared to that of g-C3N4 (88 μs), and a threefold its intrinsic structure or constructing
increase in photocurrent density (−98 μA cm−2) compared to that of g-C3N4 hybrid materials.[9] For instance, the
photocathode (−32 μA cm−2) at a potential of 0 V versus normal hydrogen transfer distance of photo-generated car-
riers can be shortened through designing
electrode (NHE) in neutral aqueous solution. The photoelectrocatalytic
2D ultrathin morphology to decrease the
performance can be further improved by fabricating Pt@g-C3N4/GDY, which photocarriers recombination in g-C3N4.[16]
displays an photocurrent of −133 μA cm−2 at a potential of 0 V versus NHE in In addition, fabricating the g-C3N4-based
neutral aqueous solution. This work provides a new strategy for the design of heterojunctions with other semiconduc-
efficient metal-free photoelectrocatalysts for water splitting. tors (such as TiO2, Bi2WO6, and CdS)
can accelerate the separation of photo-
induced electron–hole pairs through the
built-in electric field.[9] Furthermore, some
Motivated by increasing demand for renewable and clean energy noble metals (such as Pt, Ag, and Au) and metal oxides (such
source in the future, hydrogen production from water-splitting as RuO2, CoOx, and Co3O4) have been used as the cocatalysts
by solar energy has gained extensive investigations.[1–3] Among to optimize the reaction kinetics of electrons and holes for
numerous explored photocatalysts, the metal-free semiconduc- hydrogen production and oxygen production, respectively.[17]
tors, such as graphene oxide, the conjugated microporous poly- However, even though the aforementioned strategies can
mers, black phosphorus, and graphitic carbon nitride (g-C3N4), accelerate the separation and reaction of photocarriers, there
have emerged as promising candidates due to their suitable is still severe recombination during their long transfer dis-
band gap, abundance, and environment-friendly feature.[4–8] In tance, which seriously limits the photochemical conversion
particular, g-C3N4, as a typical metal-free semiconductor, has efficiency. One of the main reasons for the recombination of
attracted considerable attention in the field of photocatalytic photocarriers in g-C3N4 is that the photo-induced holes transfer
water splitting owing to its advantages of facile synthesis and much slower than photo-induced electrons,[18–21] causing inef-
fective extraction of holes from g-C3N4 into the other semicon-
ductors or cocatalysts. Therefore, it is highly desired for the
Y.-Y. Han, Dr. X.-L. Lu, S.-F. Tang, X.-P. Yin, Z.-W. Wei, Prof. T.-B. Lu design and synthesis of hybrid materials to improve the hole
Institute for New Energy Materials and Low Carbon Technologies
School of Materials Science and Engineering transfer kinetics of g-C3N4.
Tianjin University of Technology Graphdiyne (GDY), a new booming carbon material with
Tianjin 300384, China highly π-conjugated structure and high hole mobility, has
E-mail: [email protected]; [email protected] been used as a hole transfer layer in CdSe photocathode and
The ORCID identification number(s) for the author(s) of this article BiVO4 photoanode,[22,23] showing potential application in
can be found under https://doi.org/10.1002/aenm.201702992. photoelectrochemical reaction. Remarkably, GDY gains proper
DOI: 10.1002/aenm.201702992 valence band position and similar π-conjugated structure as

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g-C3N4.[22] Therefore, if 2D GDY is introduced, it can interact foil with GDY nanosheet array grown on was immersed into
with 2D g-C3N4 through the π–π stacking interaction to form a 5 mL dispersion of g-C3N4 nanosheets in NMP, and reacted
a stable ultrathin 2D/2D g-C3N4/GDY heterojunction, and the at 50 °C for 10 h in a Teflon-lined stainless steel autoclave to
photo-generated holes in g-C3N4 could be injected into GDY obtain g-C3N4/GDY.
and rapidly transfer via GDY, efficiently suppressing the photo- To view the microscopic morphology of GDY and g-C3N4/
carriers recombination. Therefore, developing a facile approach GDY, scanning electron microscopy (SEM) and transmission
to construct the ultrathin 2D/2D heterojunction of g-C3N4/ electron microscopy (TEM) images were measured. As shown
GDY, which could enhance the hole transfer rate and subse- in Figure 2a, GDY nanosheet array uniformly coats on the sur-
quently restrain the high recombination rate of photocarriers in face of Cu foil, with an irregular nanowall structure. After the
g-C3N4, is highly desired. formation of 2D/2D heterojunction of g-C3N4/GDY, the sur-
Herein, for the first time, we report a facile approach to con- face of GDY nanowall becomes wrinkled as the morphology of
struct a metal-free ultrathin 2D/2D heterojunction of g-C3N4/ g-C3N4 nanosheets (Figure 2b; Figures S2 and S3, Supporting
GDY as a photocathode for enhancing the hole transfer rate of Information). Furthermore, the TEM image of GDY nanosheets
g-C3N4, in which the 2D g-C3N4 nanosheets were decorated on (Figure 2c) is different from that of g-C3N4/GDY (Figure 2d,f),
2D GDY with 3D nanosheet array structure by a solvothermal and the 2D/2D heterojunction of g-C3N4/GDY can be clearly
reaction in N-methyl pyrrolidone (NMP) solution. The as- seen from the HR-TEM and TEM images of g-C3N4/GDY
synthesized 2D/2D heterojunction of g-C3N4/GDY provides (Figure 2e; Figure S4, Supporting Information), demonstrating
abundant transfer channels for photo-induced holes, which can the formation of 2D/2D heterojunction of g-C3N4/GDY. More-
be injected from g-C3N4 into GDY and transfer rapidly within over, from the elemental mapping for the g-C3N4/GDY hybrid
GDY due to its high hole transfer mobility, leading to a supe- nanosheets as shown in Figure 2f, it can be found that the C
rior photocurrent of −98 µA cm−2 at 0 V versus NHE in 0.1 m (red) and N (green) elements distribute uniformly on the GDY
Na2SO4 solution, threefold higher than that of as-synthesized nanosheet array as exhibited in Figure 2g–i, exhibiting the uni-
g-C3N4 photocathode (−32 µA cm−2 at 0 V vs NHE). Further- form distribution of 2D g-C3N4 on GDY nanosheet array. The
more, the photoelectrocatalytic performance can be further above images demonstrate that the g-C3N4/GDY was success-
improved by introducing Pt cocatalyst on the surface of g-C3N4 fully constructed. This unique 2D/2D heterojunction provides
in g-C3N4/GDY, due to the further optimized reaction kinetics large face-to-face interface between g-C3N4 and GDY (Figure 2e;
of photo-induced electrons, resulting in an unprecedented Figure S4, Supporting Information), as well as short distance
photocurrent of −133 µA cm−2 at 0 V versus NHE in 0.1 m and abundant channels for the transfer of photo-induced holes
Na2SO4 solution. The above results provide a new and efficient from g-C3N4 to GDY.
approach to improve the hole transfer kinetics and the photo- The structure and chemical composition of g-C3N4/GDY
catalytic activity of g-C3N4. were further investigated by the Raman spectra and X-ray
The g-C3N4/GDY was synthesized step by step, as shown in photoelectron spectroscopy (XPS). As shown in Figure 3a, the
Figure 1 and Figure S1 in the Supporting Information. First, peaks for D (1397.4 cm−1) and G (1572.1 cm−1) bands, as well
a modified Glaser–Hay coupling reaction was taken place on as the bands attributed to the conjugated diyne linkage (1927.3
the surface of Cu foil using hexaethynyl benzene as a precursor and 2181.4 cm−1) for as-synthesized GDY, are all in agreement
(see the Supporting Information),[24] and a well GDY nanosheet with those of reported GDY,[26–28] indicating the GDY nanosheet
array was grown on the surface of Cu foil after 22 h. Second, array was successfully synthesized. After the formation of
g-C3N4 was synthesized according to the literature,[25] and the g-C3N4/GDY, the peaks belonging to GDY shift toward higher
formed g-C3N4 was continuously sonicated in NMP for 20 h to wavenumbers (Figure 3b), demonstrating the π–π stacking
obtain a dispersion of 2D g-C3N4 nanosheets. Finally, the Cu interactions between GDY and electron-withdrawing g-C3N4

Figure 1. The schematic illustration for the construction of 2D/2D graphitic carbon nitride/graphdiyne heterojunction on 3D GDY nanosheet array.

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Figure 2. The SEM images for a) 3D GDY nanosheet array, and b) g-C3N4/GDY. The TEM images for c) GDY nanosheets, d) g-C3N4/GDY hybrid
nanosheets, and e) the 2D/2D heterojunction of g-C3N4/GDY (inset is the HR-TEM image for g-C3N4/GDY). f) The HADDF image for g-C3N4/GDY.
The corresponding elemental mapping images for g) C element, h) N element, and i) C and N elements.

nanosheets. The π–π stacking interactions between GDY and As shown in Figure 3c, the C1s peak of g-C3N4/GDY can also
g-C3N4 can be further confirmed by the UV–vis adsorption spec- be deconvoluted into four sub-peaks at 284.5 eV for CC (sp2),
trum for the NMP dispersion of g-C3N4/GDY, which displays 285.1 eV for CC (sp), 286.4 eV for CO, and 287.5 eV for
an obviously red absorption shift and increased absorption CO, respectively. In comparison with those peaks in GDY, the
intensity compared with those of g-C3N4 and GDY (Figure S5c, binding energies of CC (sp2) and CC (sp) in g-C3N4/GDY
Supporting Information). Interestingly, simply mixing an NMP become larger due to the π–π stacking interactions between
dispersion of g-C3N4 with GDY at room temperature cannot GDY and g-C3N4, in accordance with the results of Raman
lead to such absorption change (Figure S5c, Supporting Infor- spectra. The atomic ratio of sp/sp2 is about 2, corresponding to
mation), indicating the 2D/2D heterojunction of g-C3N4/GDY the chemical composition of graphdiyne. In addition, two peaks
via π–π stacking interactions can only be formed under heating of C 1s in g-C3N4/GDY at 287.8 and 288.4 eV can be assigned
condition. As both g-C3N4 and GDY show positive charge, as to CN (sp2) in g-C3N4, and the two peaks of N 1s in g-C3N4/
determined by the Zeta potential measurements (Figure S5d, GDY at 398.5 and 399.9 eV (Figure 3d) can be ascribed to N
Supporting Information), they are repulsive toward each other in triazine rings (sp2) and (N-(C)3) as well as (CNH) spe-
in solution, and cannot form 2D/2D heterojunction at room cies in g-C3N4, respectively.[29–31] The above results demonstrate
temperature. the g-C3N4/GDY has been successfully constructed through the
The chemical compositions of GDY and g-C3N4/GDY were π–π stacking interaction.
investigated by XPS. As shown in Figure S6 in the Supporting The electronic band structures of GDY, g-C3N4, and g-C3N4/
Information, the high-resolution XPS of C 1s in GDY exhibits GDY were evaluated by XPS valence spectra, photolumines-
four obvious peaks, in which the peaks at 284.4 and 285.0 eV cence (PL) spectra, Mott–Schottky plots and the UV–vis absorp-
can be assigned to CC (sp2) and CC (sp), respectively.[26–28] tion spectra. As shown in Figure 4a, the VB (valence band)

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Figure 3. The Raman spectra for a) GDY nanosheet array and b) g-C3N4/GDY, and the high-resolution XPS spectra for c) C 1s and d) N 1s for g-C3N4/GDY.

energy levels of g-C3N4 and GDY measured by XPS valence was conducted under dark and light using g-C3N4/GDY as a
spectra are 2.4 and 1.7 eV, respectively, the higher VB posi- photocathode in 0.1 m Na2SO4 solution. As shown in Figure 5a,
tion of g-C3N4 than that of GDY provides the hole transmis- when the light on, the potential of OCP for g-C3N4/GDY shifts
sion channel theoretically. In addition, g-C3N4/GDY shows toward a more positive potential (from 37 to 66 mV), indicating
an obvious photoluminescence quenching compared with the photo-induced holes in g-C3N4 can be indeed injected into
g-C3N4(Figure 4b), indicating the existence of GDY signifi- the VB of GDY through the 2D/2D heterojunction of g-C3N4/
cantly promotes the separation of photo-induced carriers in GDY.
g-C3N4 after the formation of 2D/2D heterojunction of g-C3N4/ Due to the effective holes extraction from g-C3N4 to GDY,
GDY.[32,33] To further analyze the band structure of g-C3N4 and the photocarrier transfer barrier of g-C3N4/GDY is reduced
GDY nanosheets, the Mott–Schottky plots were measured. As obviously, as demonstrated by the electrochemical imped-
shown in Figure 4c, the flat-band potential (corresponding to the ance spectra shown in Figure 5b. Furthermore, the life time of
conduction band) of g-C3N4 and GDY obtained from the Mott– photo-induced electron (τn) in the photocathode of g-C3N4/GDY
Schottky plots are −1.46 and −1.21 V versus Ag/AgCl, respec- can be calculated from Bode phase plots (Figure 5c) according
tively. Then the UV–vis spectra were measured for the calcula- to the following equation[34–36]
tion of band gap of g-C3N4 and GDY. As shown in Figure S7
in the Supporting Information, the band gaps of g-C3N4 and τ n = 1/( 2π f max ) (1)
GDY derived from the (αhv)2 versus photon-energy plots were
2.83 and 2.07 eV, respectively. Finally, the band structure can be The calculated electron life times in g-C3N4 and g-C3N4/
estimated by using the flat-band potentials and the calculated GDY photocathodes are 8.8 × 10−5 s and 6.1 × 10−4 s, respec-
band gaps (Figure 4d). From Figure 4d it can be found that tively. The electron life time in g-C3N4/GDY photocathode
the photo-induced holes in g-C3N4 could be injected to the VB shows about sevenfold enhancement than that in g-C3N4
of GDY, consistent with the results derived from XPS valence photocathode, demonstrating a much lower recombination
spectra (Figure 4a). rate of photo-induced electrons and holes in g-C3N4/GDY. This
To estimate whether the photo-induced holes in g-C3N4 can result clearly indicates that the hole transfer kinetics of g-C3N4
be injected into the VB of GDY, the OCP (open circuit potential) can be indeed improved by the formation of g-C3N4/GDY

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Figure 4. a) The XPS valence spectra of GDY and g-C3N4. b) Photoluminescence spectra of g-C3N4 and g-C3N4/GDY. c) Mott–Schottky plots, and
d) band structures of g-C3N4 and GDY (CB: conduction band, VB: valence band).

heterojunction, in which the GDY plays a key role in the charge g-C3N4/GDY may also affect the photoelectrocatalytic perfor-
separation process in g-C3N4/GDY due to its high hole mobility, mance, thus the samples with about 12 nm (reacted for 3 h)
and the formation of ultrathin 2D/2D g-C3N4/GDY heterojunc- and 60 nm (reacted for 20 h) thickness of g-C3N4 layer were
tion also provides multiple and efficient hole transfer channels also synthesized (Figure S8, Supporting Information), and their
from g-C3N4 to GDY. photoelectrocatalytic performance was investigated. As shown
Based on the above results, it can be expected that the as- in Figure S9 in the Supporting Information, the sample with
synthesized g-C3N4/GDY will display superior photoelectro- 24 nm thickness of g-C3N4 layer (reacted for 10 h) displays
catalytic performance than g-C3N4. Therefore, g-C3N4/GDY was the highest photoelectrocatalytic activity, which may originate
used as a photocathode, and its photoelectrochemical activity from its optimal generation and transfer distance for the photo-
for water splitting was evaluated by a three-electrode system induced carriers within 24 nm thickness of g-C3N4 layer.
in 0.1 m Na2SO4 solution. For comparison, the photoelectro- To further demonstrate the superior photoelectrocatalytic
catalytic performance of g-C3N4 and GDY was also investigated performance of g-C3N4/GDY photocathode, the photocurrents
under the same condition. As shown in Figure 5d, the linear of different photocathodes at −0.1 V versus NHE were meas-
sweep voltammetry (LSV) curves for different photocathodes at ured. As shown in Figure S13a in the Supporting Informa-
a scan rate of 2 mV s−1 under dark and light were measured. tion, g-C3N4/GDY photocathode shows a much higher current
The photocurrent of g-C3N4/GDY is as high as −98 µA cm−2 at density than those of g-C3N4 and GDY, indicating the hybrid
a potential of 0 V versus NHE, about three times higher than heterojunction structure is largely contributed to the enhanced
that of as-constructed g-C3N4 photocathode (−32 µA cm−2). The photoelectrochemical performance for water splitting. The
photocurrent achieved by g-C3N4/GDY is also higher than those fast photocurrent decay at the initial illumination shown in
of other reported g-C3N4 photocathodes (0.9–50 µA cm−2).[37–45] Figure S13a in the Supporting Information can be attributed to
The results of SEM measurement for the cross section of GDY the competitive recombination of photo-induced holes and elec-
before and after coating g-C3N4 indicate that the thickness trons at the surface of g-C3N4; this phenomenon has also been
of the g-C3N4 layer covered on GDY in g-C3N4/GDY is about observed in other reported photoelectrocatalytic systems.[46,47]
24 nm (Figure S8, Supporting Information). One may con- Adding Na2S2O8 as an electron acceptor to the solution can
cern that the thickness of the g-C3N4 layer covered on GDY in improve such fast photocurrent decay (Figure S13b, Supporting

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Figure 5. a) The OCP response of g-C3N4/GDY photocathode under dark and irradiated conditions. b) The electrochemical impedance spectra of
g-C3N4 and g-C3N4/GDY photocathodes measured under light. c) The Bode phase plots of g-C3N4 and g-C3N4/GDY photocathodes. d) Linear sweep
voltammetry scanning for different photocathodes measured under dark and light.

Information), further demonstrating the fast photocurrent as-synthesized g-C3N4/GDY is a state-of-the-art metal-free photo­­
decay originates from the charge recombination rather than the electrochemical catalyst for water splitting.
degradation of g-C3N4/GDY. Considering the mechanism of photocatalytic reactions,
To evaluate the stability of g-C3N4/GDY photocathode, if a cocatalyst for hydrogen evolution was further decorated
the chronoamperometric curve under light was carried out. on g-C3N4, there would form an elegantly sandwich-like
As shown in Figure S10 in the Supporting Information, the structure, which could realize a dual control for both reac-
g-C3N4/GDY photocathode maintains almost constant current tion kinetics of photo-induced electrons and transfer rate of
density of -300 µA cm−2 at a potential of −0.4 V versus NHE photo-induced holes in g-C3N4. To prove this assumption, the
within 7 h, suggesting the good stability of g-C3N4/GDY photo- Pt nanoparticles were deposited on the g-C3N4 nanosheets
cathode. The SEM, Raman spectra, and electrochemical imped- according to the literature method,[48] and a Pt@g-C3N4/GDY
ance spectra for g-C3N4/GDY photocathode after the stability sandwich-like hybrid material was successfully constructed
test were measured, and the results are shown in Figure S14 (Figure S11, Supporting Information). The photoelectrocata-
in the Supporting Information. From Figure S14 in the Sup- lytic performance of Pt@g-C3N4/GDY photocathode was also
porting Information, it can be found that the morphology, evaluated by PL spectra, electrochemical impedance spectra
Raman spectra, and electrochemical impedance spectra are as well as corresponding Bode phase plots (Figure S12, Sup-
all similar before and after the photocatalytic reaction, further porting Information). The life time of photo-induced electron
demonstrating the high stability of g-C3N4/GDY catalyst. After (τn) in Pt@g-C3N4/GDY was calculated from Bode phase plots
1.151 C charges passed through the external circuit, the amount (Figure S12c, Supporting Information) to be 3.18 × 10−3 s,
of 5.6 µmol of hydrogen was estimated by Gas chromatography, which is fivefold longer than that in g-C3N4/GDY photo-
and a Faradic efficiency of 93% was obtained. In addition, the cathode (6.1 × 10−4 s), demonstrating the recombination rate
incident photon-to-current efficiency (IPCE) for g-C3N4/GDY of photocarriers in g-C3N4 can be further decreased after
and g-C3N4 photocathodes were measured (Figure S15, Sup- depositing the Pt nanoparticles on g-C3N4. The increased
porting Information), the results indicate the IPCEs are much current density in photocurrent (Figure S13a, Supporting Infor-
enhanced after the formation of g-C3N4/GDY heterojunction. mation) confirmed the successful regulation of the photo­
Based on the above results, it can be demonstrated that the carriers by dual-control of both transfer rate of photo-induced

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holes and the reaction kinetics of photo-induced electrons in Keywords

g-C3N4. As shown in the LSV plots of photocathodes (Figure S13c,
graphdiyne, graphitic carbon nitride, hole transfer, photoelectrocatalysts,
Supporting Information), the photocurrent of Pt@g-C3N4/GDY
water splitting
is −133 µA cm−2 at a potential of 0 V versus NHE in 0.1 m
Na2SO4 solution, much larger than that of g-C3N4/GDY Received: October 27, 2017
(−98 µA cm−2). About 8.8 µmol of hydrogen was produced on Revised: December 4, 2017
Pt@g-C3N4/GDY when 1.793 C charges passed through the Published online:
external circuit, with a Faradic efficiency of 95%. As summa-
rized in Table S1 in the Supporting Information, the photo-
currents achieved by g-C3N4/GDY and Pt@g-C3N4/GDY are
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