Crystalline Red Phosphorus Nanoribbons: Large-Scale Synthesis and Electrochemical Nitrogen Fixation

Article abstract of DOI:10.1002/anie.202006679

Two dimensional (2D) nanoribbons constitute an emerging nanoarchitecture for advanced microelectronics and energy conversion due to the stronger size confinement effects compared to traditional nanosheets. Triclinic crystalline red phosphorus (cRP) composed by a layered structure is a promising 2D phosphorus allotrope and the tube-like substructure is beneficial to the construction of nanoribbons. In this work, few-layer cRP nanoribbons are synthesized and the effectiveness in the electrochemical nitrogen reduction reaction (NRR) is investigated. An iodine-assisted chemical vapor transport (CVT) method is developed to synthesize circa 10 g of bulk cRP lumps with a yield of over 99 percent. With the aid of probe ultrasonic treatment, high-quality cRP microcrystals are exfoliated into few-layer nanoribbons (cRP NRs) with large aspect ratios. As non-metallic materials, cRP NRs are suitable for the electrochemical nitrogen reduction reaction. The ammonia yield is 15.4 μg h^?1 mg_cat.^?1 at ?0.4 V vs. reversible hydrogen electrode in a neutral electrolyte under ambient conditions and the Faradaic efficiency is 9.4 percent at ?0.2 V. Not only is cRP a promising catalyst, but also the novel strategy expands the application of phosphorus-based 2D structures beyond that of traditional nanosheets.

Full text of DOI:10.1002/anie.202006679

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Crystalline Red Phosphorus Nanoribbons: Large-Scale Synthesis
and Electrochemical Nitrogen Fixation
Authors: Qian Liu, Xue Zhang, Jiahong Wang, Yanli Zhang, Shi Bian,
Ziqiang Cheng, Ning Kang, Hao Huang, Shuang Gu, Yun
Wang, Danni Liu, Paul K. Chu, and Xue-Feng Yu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202006679
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Crystalline Red Phosphorus Nanoribbons: Large-Scale Synthesis
and Electrochemical Nitrogen Fixation
Qian Liu,‡[a] Xue Zhang,‡[a] Jiahong Wang,*[a,b], Yanli Zhang, Shi Bian, Ziqiang Cheng, Ning Kang,
[a]
[a]
[a]
[a]
[
a]
[a]
[a]
[a]
[b]
*[a]
Hao Huang, Shuang Gu, Yun Wang, Danni Liu, Paul K. Chu, and Xue-Feng Yu
Abstract: Two dimensional (2D) nanoribbons constitute an
emerging nanoarchitecture for advanced microelectronics and
energy conversion due to the stronger size confinement effects
have aroused enormous interest since the discovery of black
phosphorus (BP) as a 2D direct bandgap semiconductor.[ It
has been applied in many fields, such as optoelectronics, battery,
catalysis and sensor. Recently, BP has been proved to be an
active electro-[9] or photo-electro-catalyst[10] for NRR. Besides
BP, other 2D phosphorus materials such as violet phosphorus[
and blue phosphorus[12,13] have great potential in photo-
electronics,[14] batteries,[15,16] and catalysis.[17,18] However, it is
difficult to produce these 2D phosphorus materials including BP
on a large scale thus hampering the development of 2D
phosphorus nanoribbons. As a phosphorus allotrope, triclinic
crystalline red phosphorus has a layered structure and the
8]
compared to traditional nanosheets.
phosphorus (cRP) composed by a layered structure is a promising
D phosphorus allotrope and the tube-like substructure is beneficial
Triclinic crystalline red
11]
2
to the construction of nanoribbons. In this work, few-layer cRP
nanoribbons are synthesized and the effectiveness in the
electrochemical nitrogen reduction reaction (NRR) is investigated.
An iodine-assisted chemical vapor transport (CVT) method is
developed to synthesize ~10 g of bulk cRP lumps with a yield of over
99%. With the aid of probe ultrasonic treatment, high-quality cRP
[
19-
microcrystals are exfoliated into few-layer nanoribbons (cRP NRs)
with large aspect ratios. As non-metallic materials, cRP NRs are
suitable for the electrochemical nitrogen reduction reaction. The
primary unit structure consists of two coupled five atom rings.
2
1]
The unique atomic configuration produces semiconducting
characteristics, anisotropy, and low-coordinated sites, and so it
is possible to convert cRP into nanoribbons with distinctive
-
1
-1
ammonia yield is 15.4 μg h mgcat. at -0.4 V vs. reversible hydrogen
electrode in a neutral electrolyte under ambient conditions and the
Faradaic efficiency is 9.4% at -0.2 V. Not only is cRP promising
catalyst, but also the novel strategy expands the application of
phosphorus-based 2D structures beyond that of traditional
nanosheets.
properties.
However, development of cRP and cRP
nanoribbons is still in the early stage due to the lack of efficient
large-scale synthesis methods.
In this work, high-quality cRP lumps and corresponding few-
layer nanoribbons are synthesized on a large scale (Figure 1a).
A
low-temperature chemical vapor transport method is
developed to convert amorphous red phosphorus into cRP with
a yield of over 99%. After tip sonication, the few-layer cRP NRs
are thinner than 20 nm and micrometers long, but the width is
around 120 nm. The ammonia yield at -0.4 V vs. reversible
hydrogen electrode (RHE) is 15.4 μg h mgcat. in 0.1 M Na SO
2 4
under ambient conditions.
Two-dimensional (2D) materials with unique atomic
configurations and properties have emerged as valuable building
blocks for advanced materials. In particular, the atomically
layered nanostructures exfoliated from the bulk counterpart
exhibit strong quantum confinement effects, abundant surface
states, and anomalous physicochemical properties.[1-3] Unlike
-1
-1
traditional isotropic nanosheets with
a large lateral size,
anisotropic nanoribbons with a smaller width confined in two
particular directions have aroused increasing interest as a new
2
D nanoarchitecture.[4-6] Owing to the stronger size confinement
effect than normal nanosheets, the nanoribbons often have new
electronic structures, directional transport properties, enhanced
anisotropic physical properties, and specific edge effects
spurring new applications in photo-electronic devices and
energy conversion.[7] Hence, it is essential to develop new 2D
nanoribbons with the desirable properties.
As an important class of 2D materials, phosphorus materials
[
[
a]
b]
Q. Liu, X. Zhang, J. Wang, Y. Zhang, Z. Cheng, K. Ning, H.
Huang, S. Gu, W. Yun, D. Liu, Prof. X.-F. Yu
Shenzhen Engineering Center for the Fabrication of Two-
Dimensional Atomic Crystals, Shenzhen Institutes of Advanced
Technology, Chinese Academy of Sciences, Shenzhen 518055, P.
R. China
E-mail: xf.yu@siat.ac.cn; jh.wang1@siat.ac.cn
Prof. P.K. Chu
Department of Physics, Department of Materials Science and
Engineering, and Department of Biomedical Engineering, City
University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong,
China
Figure 1. (a) Synthesis of cRP bulk and nanoribbons; (b) Photograph and
weight of the cRP powder; (c) Magnified photograph of the cRP powder; (d)
Photograph of the cRP ethanol dispersions before and after ultrasonication.
The cRP crystals are synthesized by a low-temperature CVT
method. The commercial amorphous red phosphorus (aRP) and
iodine (I
assistance of I
2
) are sealed in a small quartz tube and with the
, aRP is transferred from the high-temperature
2
side (480 ℃) to the low-temperature side (450 ℃), nucleates,
and crystallizes to form cRP. The reaction temperature and
annealing time are much less than those described in previous
publications (typical temperature of 550 ℃ to 650 ℃ and
†
Q. Liu and X. Zhang contributed equally to this work.
Supporting information for this article is given via a link at the end
of the document.
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Angewandte Chemie International Edition
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COMMUNICATION
annealing time of days to weeks).[11,15,22,23] After cooling to room
temperature, the dark red lumps of cRP attach to the quartz tube
wall (Figure S1a). The cRP lumps are then ground and washed
lumps. The magnified SEM image (Figure 2b) shows the
layered nature of cRP thereby making it easy to exfoliate. After
the ultrasonic treating, the interlayer vdW force and interaction
between the tube-like substructures break down so that the bulk
cRP is converted into thin nanoribbons with a width of about 120
nm and length of hundreds of nanometers to several
micrometers. As shown in Figures 2c and 2d, the aspect ratio of
most cRP NRs is larger than ten and some of them shows a
ratio of almost one hundred.
with acetone and ethanol to remove I
are obtained after drying (Figure S1b). The X-ray diffraction
XRD) pattern of the powder (Figure S1b) can be indexed to the
simulated standard pattern of triclinic phosphorus (ICSD No.
91323).[24,25] corroborating conversion of aRP to cRP. The
2
and orange-red powder
(
3
photographs and scanning electron microscope (SEM) images
in Figure S2 show that the morphologies of aRP and cRP lumps
are quite different from being disordered to regular micro-pillar-
like. To demonstrate the commercial potential of this technique,
large-scale synthesis is carried out in a double-zone tube
2
furnace with large amounts of aRP and I . The photographs of
the tube before and after synthesis in Figure S3 show complete
transform of aPR. After cleaning, grounding, washing, and
drying, about 9.937 g of the orange red powder was obtained
illustrating a high yield of more than 99% (Figure 1b, c). During
the CVT process, iodine is important in transportation and
mineralization. If the iodine is absent from the reaction, the aRP
lumps remain at the original position and no cRP is produced in
the tube (Figure S4). The phenomenon suggests that iodine
x
reacts with aRP to generate gaseous iodo-phosphopium (PI )
which is transported by the temperature gradient to the
nucleation side at a low temperature and then decomposes into
cRP and iodine. This reversible reaction continues until all the
aRP converts into cRP, which is similar to the CVT growth of
BP.[26,27]
Figure 3. (a) TEM image of cRP NRs; (b) HR-TEM image of the yellow box in
Figure 3a; (c) HR-TEM image of the blue box in Figure 3a; (d) SAED pattern of
a single cRP NR; (e, f) HAADF-STEM image and corresponding EDS element
map of cRP NRs; (g) AFM image of an individual cRP NR; (h) Thickness
distribution of cRP NRs; (i) Width distribution of cRP NRs.
The transformation from aRP lumps to cRP NRs is
investigated by XRD and Raman scattering. As shown in Figure
2
e, the XRD pattern of commercial aRP reveals amorphous
characteristics. After CVT growth, the cRP powder shows sharp
XRD peaks corresponding to triclinic phosphorus. After the cRP
powders are exfoliated into nanoribbons, the XRD peaks
broaden due to the smaller size but the positions are the same.
In the Raman spectra (Figure 2f), the change is similar to that
observed by XRD. The aRP shows three broad and weak
Figure 2. (a, b) SEM images of cRP bulk; (c, d) SEM images of cRP NRs; (e)
XRD patterns and (f) Raman scattering spectra of commercial aRP, cRP bulk,
and cRP NRs.
-1
signals between 300 and 500 cm . The Raman spectra of bulk
cRP and cRP NRs present complex vibration modes caused by
the low symmetry of the triclinic crystal and diverse atomic
coordination.[
11,28]
The sharp peaks around 353 and 368 cm
−1
Efficient synthesis of high-quality cRP crystal on a large scale
paves the way for the preparation of cRP NRs. In brief, the cRP
powder is dispersed in absolute ethanol in which the interlayer
van der Waals (vdW) interaction breaks down during probe
sonication. As shown in Figure 1d, after liquid exfoliation, the
supernatant changes from being transparent to orange. The
SEM image in Figure 2a reveals the ground cRP powder is
composed of fibers with lengths of dozens of micrometers. The
structure is quite different from that of the compact micro-pillar-
like cRP lumps (Figure S2d). The different densities manifest in
different colors, that is, orange cRP powder and dark red cRP
are related to phosphorus cage stretching vibrations in the tube-
like substructure of cRP.[28,29] Compared with bulk, the Raman
signals of cRP NRs is slightly shift to high wavenumber direction
(
Figure S5). The purity is evaluated by X-ray photoelectron
spectroscopy (XPS) (Figure S6) and energy-dispersive X-ray
spectrometer (EDS) (Figure S7). The spin splitting peaks at 129
eV and 130 eV in the high-resolution P 2p XPS spectrum of cRP
NRs arises from elemental phosphorus, whereas the weak
broad peak at 134 eV stems from slight surface oxidization
during sample transfer.[8,30] The EDS spectrum shows a small
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oxygen concentration in cRP NRs and the phosphorus purity is
higher than 92%. Moreover, in both XPS survey spectrum and
EDS analysis, there is no I element exsisted. The results
demonstrate the formation of high-purity cRP NRs and reveal
that the ultrasonic treatment only splits the weakly bound
interlayers instead of damaging the substructure.
Non-metallic materials are promising candidates for
electrochemical nitrogen fixation under ambient conditions
because they suppress competing hydrogen evolution during
nitrogen reduction.[31-35] The electrochemical nitrogen fixation
activity of cRP NRs is explored for the first time. A building unit
of two coupled five atom rings from the bulk structure with (001)
surface is adopted in the theoretical assessment (Figure 4a). To
determine the nitrogen reduction pathway and distinguish
whether the overpotential is contributed by proton or electron
transfer, the coupled proton electron transfer pathway and
sequential proton electron transfer pathway in the nitrogen
reduction reaction (NRR) are considered. All the intermediates
To further investigate the morphology and structure of cRP
NRs, transmission electron microscopy (TEM) is conducted. As
shown in Figure 3a, the weak thickness contrast suggests that
the cRP NRs are thin and the width of about 120 nm is in line
that observed by SEM. The lattice fringes in the vertical-view
high-resolution TEM (HR-TEM) image (Figure 3b) is 0.580 nm
corresponding to the (001) plane. The cross-sectional HR-TEM
image of the blue box in Figure 3a is shown in Figure 3c. The
interlayer distance observed in the cross-section TEM image is
about 1.1 nm, which is in accord with the crystal structure,[25] the
thickness of this twisted nanoribbon is ~7.8 nm. The selected-
area electron diffraction (SAED) pattern of a single nanoribbon
in Figure 3d shows that single crystal cRP NRs are formed along
the [014] axis. As shown in Figure 3e, the high-angle annular
dark-field imaging (HAADF) scanning TEM (STEM) image
reveals a thin thickness and clear edges of cRP NRs and Figure
3 3
in the first NH formation and second NH formation are shown
in Figure S9 and most of the intermediates bind with P between
two phosphorus cages. The thermodynamic triangles in Figure
S9 demonstrate that the NRR on cRP tends to proceed by the
coupled-proton electron transfer pathway (diagonal red line).
The corresponding free energy diagram is shown in Figure 4b.
*
In the first NH
3
production process, N
2
hydrogenation to NNH
are thermodynamically
and NNH * hydrogenation to NNH *
2
3
unfavorable steps with redox potentials of -0.79 V and -0.52 V,
*
*
and NNH *
) are exothermic steps with positive redox potentials of
0.40 V and 0.13 V. The reactions from N-* to second NH
are
thermodynamically favorable and occur spontaneously. The first
step of N hydrogenation to NNH* is the rate determining step
whereas NNH hydrogenation to NNH
(N + NH
3
2
3
reduction to
-
*
3
f confirms uniformly distributed phosphorus in the nanoribbons.
Atomic force microscopy (AFM) reveals that the thickness of an
individual cRP NR is 8.5 nm as shown in Figure 3g, and this
nanoribbon is about 8 layers. More AFM images are acquired
from the nanoribbons with 2 to a dozen layers of different length
3
2
due to the most negative redox potential and NRR catalysis is
expected to occur on cPR by overcoming initial hydrogenation.
The electrochemical NRR performance of cRP NRs is
investigated by loading them onto a nickel foam (cRP NRs/NF).
and presented in Figure S8.
The thickness and width
distributions of the nanoribbons are presented in Figures 3h and
3
7
i, respectively, and the thickness and width are in the range of
.5~17.5 nm and 75~175 nm, respectively. AFM corroborates
The measurement is carried out in 0.1 M Na
2 4
SO in a gastight H-
that few-layer cRP NRs are produced after liquid exfoliation.
type electrolytic cell. During the electrochemical test, purfied N
2
or Ar continuously flowed into the cathodic chamber of the
cell.[36.37] As shown in Figure 4c, the linear sweep voltammetry
(
2
LSV) curves show that the current density in the N -saturated
electrolyte is larger than that in the Ar-saturated electrolyte,
indicating that NRR may occur on cRP NRs. In order to quantify
the ammonia yield rate, chrono-amperometry electrocatalysis is
monitored at different potentials. As shown in Figure 4d, the
currents are stable during the NRR tests. After 150 min, the
amounts of NH produced at different potentials are determined
3
by the indophenol blue method. The corresponding UV-vis
chromogenic absorption spectra in Figure 4e show that the
maximum absorbance and highest NH
3
yield are observed at -
0
.4 V based on the ammonia calibration curve in Figure S11.
The NH
3
yield and Faradaic efficiency (FE) are shown in Figure
yield rate increases with the potential until -0.4 V
and then decreases when the potential is larger than -0.5 V.
4
f. The NH
3
−
1
−1
The maximum yield rate at -0.4 V is 15.4 μg·h ·mgcat. and the
maximum FE is 9.4% at -0.2 V. The NRR performance of
another elemental phosphorus, black phosphorus, is 31.37
Figure 4. (a) Structure of the unit tubular cell in cRP; (b) Free energy diagram
−1
−1
of the NRR process; (c) LSV curves of cRP NRs/NF in the Ar- and N
2
-
μg·h ·mgcat. of the NH
3
yield rate and 3.07 % of the FE at -0.7 V
saturated electrolytes; (d) Chrono-amperometry results for different applied
potentials; (e) Indophenol reagent chromogenic UV-vis absorption spectra of
(
vs. RHE).[9] In comparison, cRP NRs achieves its best
performance at a lower potential of -0.4 V, the FE of cRP NRs
also is higher than BP. These advantages may be attributed to
the more obviously anisotropy and the quasi-one-dimensional
morphology of cRP NRs, which benefit to the more efficient
charge transfer and exposing more edges sites.[11,20] The
the products obtained at different potentials; (f) NH
3
yield and Faradaic
1
15
+
efficiency cRP NRs/NF at different potentials; (g) H NMR spectra of the NH
4
and 14NH
+
4
standards and the electrochemical NRR product using cRP NRs
15
14
catalyst in the
N
2
and
2
N ; (h) Cycling test of cRP NRs/NF at -0.4 V vs. RHE.
2 4
possible byproduct of N H is also considered by the Watt-
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Angewandte Chemie International Edition
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COMMUNICATION
Chrisp method but no N
S12).
2
H
4
is observed at any potentials (Figure
Shenzhen Science and Technology Research Funding
(
JCYJ20180507182530279), Guangdong Special Support
To clarify the nitrogen origination of ammonia, control
experiments and isotope labelling experiments were
performed.[36-39] N contamination content in the gas supply was
Program (2017TX04C096), Leading Talents of Guangdong
Province Program (00201520), and City University of Hong
Kong Strategic Research Grant (SRG) No. 7005105.
-1
2
quantified as 0.0251 μg L . During the continuous N supply
test, 0.0753 μg h-1 N contamination was introduced, which is
much lower than the ammonia yield rate of 15.4 μg·h-1 per
Keywords: crystalline red phosphorus • nanoribbon • black
phosphorus • layered material • nitrogen reduction reaction
milligram catalyst. Negligible NH
that cRP NRs in Ar atmosphere at -0.4 V, N
open circuit potential (OCP), and N atmosphere for 2.5 h
without potential. The UV-vis absorption spectra of static
experiment that N was not continuously fed has no obvious
difference of continuous N supply experiment (Figure S13).
Isotope labelling experiments are conducted to certify the source
of NH
By using 15N or 14 as feeding gas, the 1H nuclear
3
was detected in experiments
2
atmosphere at the
[
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.
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magnetic resonance (NMR) spectra show doublet peaks and
triplet peaks, respectively (Figure 4g). The coupling constants of
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5
+
4
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3 Hz and 52 Hz are corresponding with the standard NH
and
1
4NH
+
, respectively[9,40,41]. Quantitative analysis of 15NH
+
1
4
4
by H
NMR spectra are carried out as well (Figure S14). The
[
[
6] D. Dass, Superlattic. Microst. 2018, 115, 88-107.
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calculated NH
3
yield rate is 15.2 μg·h ·mgcat., which is close to
the colorimetric method. These results demonstrate that NH
3
is
produced by NRR on the working electrode. The durability of
the cRP NRs/NF electrode is assessed by determining the
ammonia yield repeatedly on the same electrode and Nafion
membrane at -0.4 V. As shown in Figure 4h and Figure S15,
after five cycles, neither the NH yield rate nor corresponding FE
3
decreases. Furthermore, the current density during the long-
term electrolysis measurement for 24 hours does not change
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obviously as shown in Figure S16.
The electrochemical
measurements demonstrate stable and reliable nitrogen fixation
on cRP NRs.
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time for catalytic applications. By means of a CVT method,
high-quality cRP lumps are prepared on a large scale with a
yield of over 99%. After liquid sonication, few-layer cRP NRs
with aspect ratios larger than ten are obtained. Theoretical and
experimental investigations reveal that the cRP NRs have
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catalytic and electronic applications. Moreover, successful
fabrication of cRP nanoribbons expand the application of
phosphorus-based 2D structures beyond that of traditional
nanosheets.
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‡
[a]
‡[a]
Crystalline red phosphorus (cRP) with
a layered structure are synthesized on a
large scale by an efficient chemical vapor
transport method and few-layer 2D
nanoribbons are exfoliated. Theoretical
and experimental studies demonstrate
that the cRP nanoribbons are promising in
electrochemical nitrogen reduction in
Qian Liu,
Xue Zhang,
Jiahong
Wang,*[a,b], Yanli Zhang,[a] Shi Bian,[a]
Ziqiang Cheng,[a] Ning Kang,[a] Hao
Huang,[ Shuang Gu, Yun Wang,
a]
[a]
[a]
Dani Liu,[ Paul K. Chu,[b] and Xue-Feng
a]
*[a]
Yu
aqueous
conditions.
solutions
under
ambient
Page No. – Page No.
Crystalline Red Phosphorus
Nanoribbons: Large-Scale Synthesis
and Electrochemical Nitrogen
Fixation
This article is protected by copyright. All rights reserved.