Black Phosphorus
Black Phosphorus
Self-Archiving by Author(s)
Placed on: Osaka City University Repository
Akiyo Ozawa, Muneaki Yamamoto, Tetsuo Tanabe, Saburo Hosokawa, Tomoko Yoshida. (2020). Black
phosphorus synthesized by solvothermal reaction from red phosphorus and its catalytic activity for
water splitting. Journal of Materials Chemistry A. 8, 7368-7376. DOI:10.1039/C9TA13441G
Page 1 of 18 Journal of Materials Chemistry A
Black phosphorus synthesized by solvothermal reaction from red phosphorus and its catalytic
activity for water splitting
Akiyo Ozawa1, 2*, Muneaki Yamamoto3, Tetsuo Tanabe3, Saburo Hosokawa4, 5, Tomoko Yoshida3
1. Applied Chemistry and Bioengineering, Graduate School of Engineering, Osaka City University,
3-3-138, Sugimoto, Sumiyoshi-Ku, Osaka, Japan
2. Corporate Research Laboratories, Research & Development Division, Sakai Chemical Industry,
Co., Ltd., 5-1, Ebisujima-Cho, Sakai-Ku, Sakai, Japan
3. Osaka City University Advanced Research Institute for Natural Science and Technology,
3-3-138, Sugimoto, Sumiyoshi-Ku, Osaka, Japan
4. Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University, Kyotodaigaku
Katsura, Nishikyo-ku, Kyoto 615-8245, Japan
5. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University,
Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
*Corresponding author: [email protected], +81-72-223-4117
Abstract
We have succeeded to synthesize black phosphorus (BP) with one-pot solvothermal reaction of red
phosphorus (RP) in ethylenediamine (ED) used as a solvent. To examine the reaction mechanism, we
have investigated the influence of the synthesis conditions on BP, and the valence of dissolved
phosphorus in the solvent after the reaction. P0 species and P3+ like species are very likely dissolved
in ED as intermediates for BP production. Optimizing the reaction conditions, i.e., temperature,
charging amount of RP in ED and particle size of RP, BP was synthesized with high yield. The
synthesized BP have an extra peak at 10.2 º in X-ray diffraction pattern, which was assigned to
stacking faults or periodic distortion in direction of the c axis by simulation of diffraction. The
synthesized BP with Co-P cocatalyst showed high photocatalytic activity for hydrogen evolution from
methanol aqueous solution under visible light irradiation.
1. Introduction
Photocatalytic water splitting has attracted attention as one of the solutions to moderate global
warming.1,2 Although various metal oxides have used as photocatalysts, most of them do not work
with visible light owing to their quite wide band gap. Recently, black phosphorus (refers to as BP
hereafter) has been studied as a candidate photocatalyst working under visible light.3–6 It is a layered
semiconductor having a narrow band gap which could be altered by changing its layer thickness.7,8
The synthesis of BP is usually done at high temperature and pressure that makes the quantity synthesis
difficult. Some new synthesizing methods of BP have been developed, for examples, a ball milling
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method and chemical vapor depositions using red phosphorus (referred to as RP hereafter).9,10
However, these methods seem difficult to apply for industrial scaled production. Recently, solution
syntheses of BP suitable for mass production have attracted attention. Tian et al. have employed a
solvothermal synthesis of BP nanosheets using white phosphorus and succeeded to synthesize BP
showing high photocatalytic activity for water splitting.11 Li et al. have produced composites of RP
and BP for Li/K-ion storage from white phosphorus with the solvothermal synthesis using amine as
a solvent. They have indicated that both primary amines with –NH2 and secondary amines with –NH–
could dissolve white phosphorus making precursor in BP synthesis.12 Both studies, unfortunately,
have used white phosphorus, which is toxic and flammable above 40 °C. On the other hand, RP is
safely handled and widely used in industries. Therefore, the solution synthesis of BP using RP as
starting material, if possible, would be very important for industrial synthesis. Dragulescu-Andrasi et
al. have shown that potassium ethoxide can convert to soluble polyphosphide from RP.13 Zhao et al.
have produced agglomerates of very small BP nanosheet which have a wider band gap than RP by
hydrothermal synthesis using ammonium fluoride aqueous solution and RP as reactants.14 Liu et al.
reported that synthesis of composite of BP/RP with high photocatalytic activity for water splitting
from RP in amine solvent.15 However, there are few reports on method to get high yield of BP and
the synthesis mechanism of BP from RP were unclear.
In this study, we have applied one-pot solvothermal reaction with amines as a solvent and RP as a
starting material to synthesize BP to be used as a photocatalyst of water splitting. By optimization of
synthesis conditions in terms of concentrations and particle sizes of RP as a starting material, reaction
temperature, and time, to get high yield of BP, we have succeeded in synthesis of BP. Synthesized
BP was characterized by various methods, such as X-ray diffraction, scanning electron, and
transmission electron microscopes. To understand mechanism of BP synthesis, i.e. dissolution of RP
and precipitation of BP, P K-edge XANES spectra of filtrate, which was remained solvent after
removing product by filtration, were measured. Formation mechanism and photocatalytic activity for
hydrogen evolution were discussed.
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containing H2PtCl6 as Pt source.16 The loading amount of Pt was adjusted to be 0.5 mol% as Pt metal.
The Pt loaded BP is referred to as Pt/sample 11.
Co/sample 11 was prepared by the one-pot reaction in the same way as sample 11 adding cobalt
acetylacetonate into the solvent. Three samples were prepared changing the amount of cobalt
acetylacetonate in the solvent. The loaded amount of Co in the prepared samples were determined by
Energy Dispersive X-ray spectroscopy (EDS) of Scanning Electron Microscope (SEM) and found to
be 1.1, 2.0, 2.3 mol% as Co metal in the samples.
3. Results
3.1 Formation of BP
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two phosphorus species. Either or both species should be involved in the formation of BP, which is
discussed later.
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established. Further, the synthesized BP under the optimized condition exhibited the layered structure,
one of the most important characteristics of BP. However, it included some periodic distortion or
stacking fault, which likely inhibited BP to be larger sheet.
Discussion
1) Mass balance in synthesis and dissolution of RP in ED
Mass balance among charged RP, residue (sample), P dissolved in filtrate (ED), and produced BP
was determined after the separation of the residue and the filtrate room temperature (RT) as follows
for samples of 9, 10, 7, and 11 synthesized under the same condition except initial charged amount
of RP. After the synthesis, firstly, remained solvent and produced solid were separated by filtration.
Then the amounts of remained RP and produced BP in the residue were determined from the
respective fraction determined by X-ray analysis given in Table 1. The results are given in Table 2,
the table shows BP yield is quite high in sample 11. It is also quite important to note that P was
dissolved in ED showing a saturation concentration around 6.0 g/L suggesting the solubility limit at
RT. Since the solubility should be higher at higher temperatures, significant amount of P could be
dissolved in ED at 160 ºC. The precipitation of BP would proceed when the concentration of P in ED
became the solubility limit at the reaction temperature and also during cooling owing to the reduction
of the solubility. On the other hand, when the P concentration did not attain the solubility limit like
sample 9 in which the charged amount of P was too small, and also sample 8 in which the particle
size of charged RP is too large to be fully dissolved, the precipitation of BP would be suppressed. All
these observations confirm that the BP synthesis proceeds as, firstly RP is dissolved in ED as P0
and/or P3+ states and then BP precipitates when the concentration of P in ED becomes the saturation
level.
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2) Mechanism of BP formation
Here discussed is the precipitation mechanism of BP from P dissolved in ED. It is known that ED
dissolves some metal ions making a chelate consisting of a five-membered ring with a metal ion in
its center.24,25 In the present case, ED could be chelated with P on the surface of RP like in Fig. 9 (a),
or one NH2 is bonded to P as shown in Fig. 9 (b) and dissolved as P3+ species as supported in XANES
spectra. Considering the existence of P0 species, the P3+ species would be equilibrated with the P0
species. Li et al. reported the existence of soluble polyphosphorus (P162-) in ED.12 In this study, the
P0 species is probably making polyphosphorus like P162-. Considering these points, the nucleation of
BP may proceed through aggregation of the soluble polyphosphorus like scheme (1). It is considered
that the periodic distortion or stacking faults structure seen in XRD pattern is accompanied during the
aggregation of the polyphosphorus to relax the lattice distortion.
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BP in the chemical form of CoxP works as the cocatalyst of BP on the photocatalytic hydrogen
evolution.
As shown in Fig. 4S, the catalytic activity gradually decreased in long time use. One of the reasons
for the gradual reduction is the aggregation of loaded Co in the sample shown in Fig. S6 and S7. The
aggregation of the loaded Co is likely the cause of the reduction of the hydrogen evolution as seen in
Fig. S4. Other reasons are morphology change as seen in Fig. S5, which accompanies the widening
and lower energy shift of the main peak of P 2p in XPS spectra (Fig. S8). Since BP has high carrier
mobility in the parallel direction to the BP sheet, the morphology change appeared in Fig. S5 would
reduce the mobility of photoexcited holes and electrons resulting in the reduction of the photocatalytic
activity. For air-exposed BP, Edmonnds et al. observed a similar change in P 2p XPS spectra21, while
Island et al. observed reduction of conductance of BP31. Considering these observations, the
conductivity of the Co/sample 11 after the test was very likely decreased by degradation with
superoxide generated under photo irradiation32. The change of morphology and the reduction of
conductance were also likely to the cause of the reduction of hydrogen evolution.
Conclusions
We have succeeded in synthesizing black phosphorus (BP) employing one-pot solvothermal reaction
of red phosphorous (RP) and ethylenediamine (ED) used as a solvent. The method is safer and can
synthesize larger amounts of BP than conventional methods using white phosphorous or high pressure
and temperature. Optimizing reaction condition (reaction temperature and time, slurry concentration
and particle size of RP), BP was synthesized with quite high yield.
The synthesized BP exhibits sheet-like morphology with a fully crystalized layered structure
excepted periodic distortion or stacking faults in the direction of c-axis. However, the sheet-width or
crystalline size of the synthesized BP was not large.
The BP synthesis very likely proceeds through the dissolution of RP in ED to be P0 and/or P3+ states
and BP precipitation from dissolved P. The periodic distortion or stacking faults were very likely
introduced in the synthesis process to relax accumulated distortion and inhibit the growth of the sheet
width.
The synthesized BP showed high photocatalytic activity with an aid of Co-P cocatalyst for hydrogen
evolution from methanol aqueous solution under visible light irradiation. However, the activity
decreased after long time use owing to the aggregation of Co-P cocatalyst and morphology change of
BP.
To increase the photocatalytic activity and durability, larger sheets are preferable, because they
should have less stacking faults and terminated bonds at the sheet edge. Therefore enlargement of the
sheet width of the synthesized BP is necessary.
Conflicts of interest
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Acknowledgments
This study was supported by JSPS KAKENHI Grant Number JP16H06440 (Synthesis of Mixed
Anion Compounds toward Novel Functionalities). We thank Mr. Yuta Yamamoto in High Voltage
Electron Microscope Laboratory, Nagoya University for assistance with the HRTEM measurements.
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X-ray peak intensities of RP [a] and BP [b] were taken from X-ray diffraction peak appeared around
15.4 º and 17 º respectively. The relative yield of BP [c] was calculated as the fraction of b to a + b.
Crystal sizes [d] were calculated from the 020 peak of BP. For some samples, their crystal size are
not given owing to large uncertainty in determination. Note samples 3 and 7 are duplicated for easy
comparison.
Table 2. Mass balance among charged RP, residue after filtration (sample), P dissolved in filtrate
(ED), produced BP in residue, and BP yield for samples 9, 10, 7, and 11 given in Table 1.
Sample RP initially charged (mg) Residue P dissolved in filtrate (ED) (mg) Produced BP BP
No. (Slurry concentration (g/L)) (sample) (mg) (Concentration (g/L)) in residue (mg) yield (%)
75 60
9 (3.75) 15 (3.0) 0.6 0.8
150 113.1
10 (7.5) 36.9 (5.7) 13.5 9.0
300 109.3
7 (15) 190.7 (5.5) 181.0 60.3
600 121
11 (30) 479 (6.1) 463.9 77.3
Journal of Materials Chemistry A Page 12 of 18
500 nm 500 nm
Fig. 1. SEM images of RP and the synthesized samples under different slurry
concentrations. a) RP with 68 μm, b) sample 9, c) sample 10, d) sample 7, and e) sample
11. The scale bars in each figure are 500 nm.
Fig. 2. XRD pattern of the samples respective to the SEM images in Fig. 1. Reference
pattern of PDF076-1976 in JCPDF card is given for comparison. Peak marked with asterisk
are unidentified.
Page 13 of 18 Journal of Materials Chemistry A
Fig. 3. UV-vis diffused reflectance spectra of the samples respective to the SEM images in
Fig. 1.
(a) (b)
P
8.7 Å
(c) (d)
Fig. 5. (a) Unit cell of crystalline BP, (b) proposed crystal structure image of the sample 7.
(c) and (d) are simulations of X-ray diffraction patterns corresponding respectively to (a)
and (b) performed by VESTA program. (d) was simulated with vacancy. In the simulation,
periodic stacking faults in (b) is assumed to be caused by vacancies.
Page 15 of 18 Journal of Materials Chemistry A
Fig. 8. Hydrogen evolution in water splitting with methanol aqueous solution under visible
light irradiation for, a) bare sample 11(triangle), b) Pt/RP (circle), c) Pt/sample 11(square),
and d) Co/sample 11(diamond).
(b)
(a)
RP
a) Pt 4f b) Co 2p Co-P
Pt04f7/2 Co 2p3/2
Pt0 4f5/2
Intensity (a. u.)
Fig. 10. a) Pt 4f XPS spectrum of Pt/sample 11, b) Co 2p XPS spectrum of Co/sample 11.
Page 18 of 18
Red P
Co2+
160 °C
Black P Visible
H2 light
H+