Direct Z-Scheme Hetero-phase Junction of Black/Red Phosphorus for Photocatalytic Water Splitting

Article abstract of DOI:10.1002/anie.201906416

Black phosphorus (BP) has recently drawn attention in photocatalysis for its optical properties. However, limited by the rapid recombination of photogenerated carriers, the use of BP for photocatalytic water splitting still remains a huge challenge. Herein, we prepare a black/red phosphorus (BP/RP) hetero-phase junction photocatalyst by a wet-chemistry method to promote the interfacial charge separation and thus achieve Z-scheme photocatalytic water splitting without using sacrificial agents. The Z-scheme mechanism was confirmed by time-resolved transient absorption spectroscopy. This work provides a novel insight into the interface design of hetero-phase junction with atomic precision.

Full text of DOI:10.1002/anie.201906416

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Direct Z-Scheme Hetero-phase Junction of Black/Red
Phosphorus for Photocatalytic Water Splitting
Authors: Fulai Liu, Rui Shi, Zhuan Wang, Yuxiang Weng, Chi-Ming
Che, and Yong Chen
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201906416
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Direct Z-Scheme Hetero-phase Junction of Black/Red
Phosphorus for Photocatalytic Water Splitting
Fulai Liu,[a,c] Rui Shi,[a] Zhuan Wang,[b] Yuxiang Weng,[b,c] Chi-Ming Che[d] and Yong Chen*[a,c]
Abstract: Black phosphorus (BP) has recently drawn tremendous
attention in photocatalysis for its excellent optical properties.
However, limited by the rapid recombination of photogenerated
carriers, the use of BP for photocatalytic water splitting still remains
a huge challenge. Herein, we fabricate a black/red phosphorus
(BP/RP) hetero-phase junction photocatalyst by a wet-chemistry
method to successfully promote the interfacial charge separation
and thus achieve Z-scheme photocatalytic water splitting without
using sacrificial agents. The Z-scheme mechanism was
unambiguously confirmed by time-resolved transient absorption
spectroscopy. This work provides a novel insight into the interface
design of hetero-phase junction with atomic precision.
enables BP as an efficient photocatalyst for water splitting with
wide response in the solar light spectrum.[4] However, due to the
rapid recombination of photogenerated carriers, the observed H2
evolution rate by bare BP is very low.[5] To overcome this
drawback, BP-based heterostructure systems have been proved
to be effective for boosting the separation of photogenerated
carriers.[6] Particularly, the construction of Z-scheme systems
can not only achieve complementary light absorption and
efficient separation of photogenerated carriers, but also reserve
their strong photoredox properties for catalytic reactions.[7]
However, the construction of Z-scheme based on exfoliated BP
nanosheets still suffers from the following issues: 1) the
preparation of BP nanosheets from bulk BP is a complicated and
time-consuming process; 2) low charge transfer efficiency
between the different semiconductors due to poor interface
contacts.
Herein, we design and construct a BP/RP hetero-phase
junction photocatalyst by a one-step wet-chemistry method. The
two semiconductors for hetero-phase junction have the same
chemical composition but different crystal lattices, therefore
providing an opportunity to build a perfect interface with atomic
precision. We note that this strategy has been previously used to
promote charge separation in both anatase-rutile TiO2 and -
Ga2O3 hetero-phase junction.[8] In our current case, the BP/RP
photocatalysts are successfully obtained and can be well-
dispersed in water to achieve efficient visible light-driven Z-
scheme water splitting without using any sacrificial agents.
Solar-to-hydrogen (H2) conversion has been considered as an
attractive and sustainable technique to solve the environmental
issues and global energy crisis. Since the pioneer work reported
by Fujishima and Honda on photoelectrochemical water splitting
using a TiO2 electrode,[1] various semiconductor photocatalysts
have been explored in this field. In particular, metal-free
photocatalysts such as graphitic carbon nitride (g-C3N4), have
attracted increasing attention in recent years, because they are
generally earth abundant, low toxic and environmentally
friendly.[2] However, the solar-to-hydrogen efficiency of these
photocatalysts is still far from the threshold of industrial
applications. Therefore, it is highly desired to develop novel
metal-free high-performance photocatalysts for water splitting.
Recently, black phosphorus (BP), as an emerging 2D
material, has shown promising potential in photocatalytic solar
energy conversion owing to its anisotropic layered structure,
layer-dependent direct bandgap, and superior carrier migration
characteristics.[3] Especially, the adjustable direct-band-gap
Benefiting from their appropriate band structures with
a
staggered alignment and high-quality interfacial contacts forming
from the in situ growth of BP into the matrix of RP, the efficient
separation and transfer of photogenerated electrons and holes
can be realized and thus enable the water reduction and
oxidation reactions to occur in BP and RP, respectively.
The BP/RP hetero-phase junction was in situ constructed
with bulk RP as a feedstock and ethylenediamine as the solvent
(Scheme S1, Supporting Information). The detailed experimental
procedures and optimal reaction conditions are provided in the
Supporting Information (Figure S1 and S2, Table S1). It should
be stressed that solvents play a crucial role in the phase
transformation process. The RP transformed to BP successfully
only in primary diamine solvents (for example, ethylenediamine
and diethylenetriamine) but failed in solvents including H2O,
alcohols and other amines. We infer that the polymeric RP chain
can be expanded, activated and cleaved by the intercalation
effect of diamine solvents.[9] The energy-dispersive X-ray (EDX)
results show that the products mainly consist of P element
(Figure S3). Further, Raman spectra prove that both RP and BP
exist in the hetero-phase junction. As shown in Figure 1a, three
characteristic peaks of BP are found at 361.5, 443.4 and 470.2
[a]
F. L. Liu, Dr. R. Shi, Prof. Dr. Y. Chen
Key Laboratory of Photochemical Conversion and Optoelectronic
Materials & HKU-CAS Joint Laboratory on New Materials
Technical Institute of Physics and Chemistry
Chinese Academy of Sciences
Beijing 100190, P. R. China
E-mail: chenyong@mail.ipc.ac.cn
Dr. Z. Wang, Prof. Dr. Y. Weng
Beijing National Laboratory for Condensed Matter Physics & CAS
Key Laboratory of Soft Matter Physics
Institute of Physics
Chinese Academy of Sciences
Beijing 100190, P. R. China
F. L. Liu, Prof. Dr. Y. Weng, Prof. Dr. Y. Chen
University of Chinese Academy of Sciences
Beijing 100049, P. R. China
[b]
[c]
[d]
Prof. Dr. C. M. Che
State Key Laboratory of Synthetic Chemistry & Department of
Chemistry, The University of Hong Kong
Pokfulam Road, Hong Kong SAR, P. R. China
1
2
cm−1, attributed to the Ag (out-of-plane mode), B2g and Ag (in-
plane mode) of BP, respectively.[10] And the peaks at 345.7,
385.2-400.8 and 451.3 cm−1 can be indexed to the fundamental
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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mode (B1), symmetric stretch modes (A1) and degenerate mode
(E1) of RP, respectively.[11] Based on thermogravimetric analysis
(TGA), the content of BP is estimated to be about 10 wt%
(Figure S4).[12] Due to the amorphous nature of RP, X-ray
diffraction (XRD) patterns of the as-prepared samples only
display the characteristic of orthorhombic (Cmca) crystal
structure of BP (JCPDS no. 76-1967) (Figure 1b).[13]
Then, the light-harvesting capability of the BP/RP hetero-
phase junction was investigated by UV-Vis diffuse reflectance
spectra (DRS). As shown in Figure 2a, the absorption edge of
RP appears at about 680 nm, while BP nanosheets display a
very wide absorption from the UV to NIR region with absorption
edge located at about 1000 nm. For the BP/RP hetero-phase
junction, the absorption edge extends to 900 nm with intense tail
absorption in the NIR region. Compared with RP, the absorption
edge of BP/RP exhibits an obvious redshift, which reveals a
strong interfacial interaction between BP and RP in the BP/RP
hetero-phase junction.[6c, 7d]
Figure 1. a) XRD patterns, b) Raman spectra, c) TEM image and d) HRTEM
image of the BP/RP hetero-phase junction, inset: a high-resolution magnified
picture.
Figure 2. a) UV-vis DRS spectra. b) UPS spectra. c) The energy band offsets
diagram and hetero-phase junction interface charge property. d) Schematic
illustration of direct Z-scheme charge transfer pathway.
The morphologies of the as-prepared BP/RP hetero-phase
junction were characterized by transmission electron microscopy
(TEM) and atomic force microscopy (AFM). TEM images clearly
show an ultrathin sheet-like structure with size ranging from 50
to 200 nm (Figure 1c and S5). AFM images reveal that the
samples possess a thickness of about 6 nm (Figure S6). High-
resolution TEM analysis gives direct evidence for the formation
of hetero-phase junction. The distinct lattice fringes are
observed with a d-spacing of 0.258 nm, assigned to (040)
planes of BP crystal (Figure 1d).[14] Obviously, high-quality
interfacial contacts are formed in BP/RP hetero-phase junction,
in which crystallized BP interlaced with amorphous RP. Such
phase junction is achieved by covalent bonds at the atomic level
rather than van der Waals forces, which can maximize the
separation and transfer of photogenerated carriers.
Appropriately aligned band structures are critical to achieve
photocatalytic water splitting. We thus take use of Tauc plots
and ultraviolet photoelectron spectra (UPS) to determine the
band structures of BP and RP. Based on Tauc plot equation:
[(h)2 = A(h-Eg)], the band gap values (Eg) of BP and RP
nanosheets are estimated to be about 1.27 and 1.96 eV,
respectively (Figure S10). The UPS spectra of BP and RP
nanosheets are shown in Figure 2b. According to the linear
intersection method, the maximum valence band values (EVB) of
BP and RP are determined to be 0.86 and 1.76 V (vs. NHE),
respectively (Figure S11).[16] Correspondingly, the conduction
band values (ECB) of the BP and RP are –0.41 and –0.20 V
(vs.NHE) by formula ECB = EVB - Eg.
To further determine the chemical composition of the BP/RP
hetero-phase junction, we measured its X-ray photoelectron
spectroscopy (XPS) and Fourier transform infrared spectroscopy
(FT-IR). The XPS survey spectrum affirms the main existence of
elemental P in BP/RP (Figure S7a). High-resolution P2p XPS
spectra show two narrow peaks located at 129.6 and 130.5 eV,
which are assigned to elemental P 2p3/2 and 2p1/2 (Figure
S7b).[15] A weak and broad sub-band for oxidized phosphorus
species (PxOy) is apparent at ~133.2 eV, which is also confirmed
by the corresponding FT-IR spectra (Figure S8).[5b] These results
imply that partial oxidation happened on the surface of BP/RP, in
accordance with its low zeta potential value of –39.2 mV (Table
S2). Note that the moderate surface oxidation can enhance the
hydrophilicity and dispersibility of samples in water (Figure S9).
Meanwhile, the work functions () of BP and RP are
determined to be about 3.34 and 4.11 eV, respectively (Figure
S10). Since the charge transfer process at the interface of two
semiconductors is dependent on their work functions, the
electrons in BP will flow to RP through the hetero-phase junction
until their Fermi levels reach an equilibrium,[7c, 17] Hence, the BP
layer will remain positive charges, and accordingly, the RP layer
will accumulate negative charges (Figure 2c). Consequently, an
internal built-in electric field directed from RP to BP at the phase
junction interface is formed, which benefits the separation and
transfer of photogenerated carriers via the Z-scheme pathway.
Adversely, a traditional type II charge transfer pathway requires
more energy due to band bending and internal electric field,
which is not conducive to continual charge transfer in
thermodynamics (Figure S12). The BP/RP hetero-phase junction
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with Z-scheme charge transfer pathway can also be supported
by photoelectrochemical measurements (Figure S13).[18]
According to the aforementioned results, the energy band
alignment of BP can match well with RP to form a valid direct Z-
scheme photocatalytic system (Figure 2d). The photogenerated
electrons in the CB of RP can readily recombine with the
photogenerated holes in the VB of BP at the hetero-phase
junction interface. As a result, the strong reducibility of electron
in the CB of BP and oxidizability of holes in the VB of RP are
retained to drive redox reactions.
circuit potential decay curves (OCP), were also carried out to
testify the charge separation in the BP/RP hetero-phase junction
by Z-scheme pathway (Figure S16–S18, Table S4).
To thoroughly clarify the efficient interfacial charge transfer
within the hetero-phase junction via a direct Z-scheme pathway,
time-resolved transient absorption spectra (TAS) of samples
were performed under 400 nm excitation to track the real-time
photogenerated carrier dynamics.[6c, 7d, 19] Usually, the surface-
trapped electrons peaks of TAS are at 500-1500 nm.[7d, 20] As
shown in Figures 3a-c, broad absorption bands centered at 550
nm were observed, the concentration of photogenerated carrier
decayed in a multi-exponential manner because of charge
recombination.
Figure 4. a) Photocatalytic H2 production over various samples. b) The rate of
H2 production over BP/RP hetero-phase junction with different non-noble
metals incorporation. c) Photocatalytic durability test and d) EPR spectra.
The photocatalytic performance of the samples was
evaluated in pure water without using any sacrificial agents. As
shown in Figure 4a and Figure S19, pristine BP does not show
H2 production activity, while BP/RP hetero-phase junction has
excellent H2 production activity (0.33 mmol g-1 h-1), 3.3 and 2.5
times higher than that of RP and the mixture of BP and RP,
respectively, indicating the potential of the hetero-phase junction
with Z-scheme pathway for achieving high performance of water
splitting. Delightedly, when a certain amount of non-noble metals
are loaded as cocatalyst, the H2 evolution activity is improved
significantly, and 1.4 wt% Co-incorporated BP/RP hetero-phase
junction achieves the maximum activity (2.96 mmolg-1h-1)
(Figure 4b, S20, S21). Moreover, the apparent quantum
efficiency (AQE) reaches up to 1.21% at 420 nm. In addition, the
Co-incorporated BP/RP still retains 82% of its initial
photocatalytic activity after four cycles (Figure 4c). The Raman
spectra of the BP/RP hetero-phase junction after photocatalytic
reaction showed no obvious change (Figure S22),
demonstrating the good stability of our photocatalytic system.
We then analyzed the oxidation species produced from
photogenerated holes during the water splitting reaction.
Surprisingly, O2 was not detected. Instead, oxidized species •OH
Figure 3. TAS measurements: a) BP, b) RP and c) BP/RP after irradiation with
a 400 nm laser flash, d) time profiles of normalized TAS at 550 nm.
To estimate the decay kinetics of photo-generated carrier in
the samples, the time profiles of the TAS probed at 550 nm were
fitted by a two-exponential function (Figure 3d), and their fitting
parameters were summarized in Table S3. Generally, the short
lifetime (1) and long lifetime (2) components result from
electrons trapped at shallow and deep sites before their
recombination.[19c] Considering the main content (90 wt%) of RP
in the as-prepared samples, the TAS signals of BP/RP are
mainly attributed to excited RP. Compared to pure RP (1: 15.9
ps; 2: 315.2 ps), the decay lifetimes of BP/RP hetero-phase
junction are largely decreased to 6.5 ps (2%) and 166.2 ps
(98%), owing to the existence of an additional channel of
interfacial electron transfer from CB of excited RP to the VB of
radicals and H2O2 were identified through
a series of
spectroscopic experiments. The characteristic quartet peaks of
DMPO-•OH adducts in the BP/RP suspension were detected
through in situ EPR spectra (Figure 4d), suggesting the single-
electron oxidation of water to produce •OH by photogenerated
holes. Meanwhile, photoluminescence spectrum also proved the
appearance of •OH radicals (Figure S23). As the photocatalytic
reaction proceeded, a small amount of H2O2 was also detected
(Figure S24). We tentatively attribute the formation of H2O2 to
the combination of two •OH.[22] Although the valence band
position of the materials is positive enough for the formation of
O2 and H2O2, compared to the concerted four-electron process
for O2 evolution, these species formed H2O2 via the two-electron
process is kinetically more favorable.[23] Additionally, trace
adjacent BP (Figure S14). Similar phenomena have been
19a, 19c]
observed in previous reports.[7d,
Meantime, the rate of
electron transfer from RP into BP is calculated to be 2.9 × 109 s-1
(Table S3).[19a,
Upon decreasing the content of BP, the
21]
electron transfer rate is slower (Figure S15). A series of
phoelectrochemical (PEC) measurements including photocurrent
response, electrochemical impedance spectra (EIS) and open-
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In summary, direct Z-scheme hetero-phase junction of
BP/RP is successfully constructed by an in situ wet-chemistry
method and unambiguously confirmed by various spectroscopic
and electrochemical measurements. Benefiting from their
appropriate band structures with a staggered alignment and
perfect phase junction interface, the efficient separation and
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Acknowledgements
This work is supported by the Strategic Priority Research
Program of the Chinese Academy of Sciences (XDB17000000),
the Natural Science Foundation of China (21773275, 21633015,
11721404) and the Ministry of Science and Technology
(2018YFA0208701). Y.C. thanks the financial support from K.C.
Wong Education Foundation and CAS-Croucher Funding
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Keywords: Black Phosphorus • Phase Junction • Z-scheme •
Photocatalysis • Water Splitting
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Entry for the Table of Contents
COMMUNICATION
A
direct Z-scheme hetero-phase
Fulai Liu, Rui Shi, Zhuan Wang, Yuxiang
Weng, Chi-Ming Che and Yong Chen*
junction of BP/RP photocatalyst is
prepared by a wet-chemistry method.
Benefiting from their appropriate band
structures with a staggered alignment
and perfect phase junction interface,
the BP/RP hetero-phase junction
exhibits
photogenerated carriers and achieves
Z-scheme photocatalytic water
Page No. – Page No.
Direct Z-Scheme Hetero-phase
Junction of Black/Red Phosphorus
for Photocatalytic Water Splitting
efficient
separation
of
splitting without using sacrificial
agents.
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