Phosphorus-Doped Carbon Nitride Tubes with a Layered Micro-nanostructure for Enhanced Visible-Light Photocatalytic Hydrogen Evolution

Article abstract of DOI:10.1002/anie.201508505

Phosphorus-doped hexagonal tubular carbon nitride (P-TCN) with the layered stacking structure was obtained from a hexagonal rod-like single crystal supramolecular precursor (monoclinic, C2/m). The production process of P-TCN involves two steps: 1) the precursor was prepared by self-assembly of melamine with cyanuric acid from in situ hydrolysis of melamine under phosphorous acid-assisted hydrothermal conditions; 2) the pyrolysis was initiated at the center of precursor under heating, thus giving the hexagonal P-TCN. The tubular structure favors the enhancement of light scattering and active sites. Meanwhile, the introduction of phosphorus leads to a narrow band gap and increased electric conductivity. Thus, the P-TCN exhibited a high hydrogen evolution rate of 67 μmol h^-1 (0.1 g catalyst, λ >420 nm) in the presence of sacrificial agents, and an apparent quantum efficiency of 5.68 % at 420 nm, which is better than most of bulk g-C₃N₄ reported. Phosphorus-doped hexagonal carbon nitride tubes were obtained from a rod-like supramolecular precursor through phosphorous acid assisted hydrothermal and subsequent thermal treatment. It exhibits a high visible-light photocatalytic hydrogen evolution performance that is better than most reported bulk carbon nitrides, which is due to the hierarchical micro-nanostructure and P doping.

Full text of DOI:10.1002/anie.201508505

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International Edition: DOI: 10.1002/anie.201508505
German Edition: DOI: 10.1002/ange.201508505
Hydrogen Evolution Catalysts
Phosphorus-Doped Carbon Nitride Tubes with a Layered Micro-
nanostructure for Enhanced Visible-Light Photocatalytic Hydrogen
Evolution
Shien Guo, Zhaopeng Deng, Mingxia Li, Baojiang Jiang,* Chungui Tian, Qingjiang Pan, and
Honggang Fu*
Abstract: Phosphorus-doped hexagonal tubular carbon
nitride (P-TCN) with the layered stacking structure was
obtained from a hexagonal rod-like single crystal supramolec-
ular precursor (monoclinic, C2/m). The production process of
P-TCN involves two steps: 1) the precursor was prepared by
self-assembly of melamine with cyanuric acid from in situ
hydrolysis of melamine under phosphorous acid-assisted
hydrothermal conditions; 2) the pyrolysis was initiated at the
center of precursor under heating, thus giving the hexagonal P-
TCN. The tubular structure favors the enhancement of light
scattering and active sites. Meanwhile, the introduction of
phosphorus leads to a narrow band gap and increased electric
conductivity. Thus, the P-TCN exhibited a high hydrogen
to remove the template and prohibits further functionaliza-
tion. Besides that, the chemical doped GCN with foreign
elements, such as phosphorus and sulfur, can tune the energy
band structure and conductivity of GCN, thus enhancing the
visible-light photocatalytic quantum efficiency as well as
improving their surface properties of GCN. This means that
the GCN with novel hierarchical micro-nanostructure and
simultaneous nonmetal element doping by the template-free
method is highly desirable but poses challenges.
[8]
To date, self-assembled supermolecular precursors by
hydrogen bonding among molecules have emerged as
a potential selection to prepare specially-shaped micro-nano
materials, as hydrogen bonding has strong direction and
À1
[9]
evolution rate of 67 mmolh (0.1 g catalyst, l > 420 nm) in the
saturation. The ordered and hollow GCN structures had
presence of sacrificial agents, and an apparent quantum
efficiency of 5.68% at 420 nm, which is better than most of
bulk g-C N reported.
been synthesized using the cyanuric acid-melamine complex
[10]
as a starting material. The GCN microspheres and micro-
sheets were also prepared using similar method by controlling
precipitation temperature and selecting proper organic sol-
3
4
[11]
G
raphitic carbon nitride (g-C N , labeled GCN), as a metal-
vents.
The supramolecular precursors mentioned above
3
4
free organic semiconductor, has attracted increasing attention
because it possesses high thermal and chemical stability and
were mainly produced by the assembly of two or more
components under organic solvents. Undoubtedly, use of
water solvent is more beneficial to molecule self-assembly
based on hydrogen bonding, forming the stable, large-sized,
and regular supramolecular precursors. It is well known that
melamine could be transformed into cyanuric acid at a suit-
[1]
an appealing electronic structure. These unique properties
of GCN allow for its diverse applications, such as photo-
catalytic hydrogen evolution, the oxygen reduction reaction
[2–4]
(
ORR), and oxygen evolution reaction (OER).
Bulk GCN
[12]
obtained by the direct thermal polymerization process gen-
erally yields relatively low surface areas and less active sites
able pH value. It would be desirable that supramolecular
precursor can be synthesized in situ from a single melamine
molecular source using acidic aqueous solution like phos-
phorous acid. The phosphorous acid not only could adjust pH
value to prompt the hydrolysis of melamine into cyanuric
acid, but also provide potential P source for the P-doping on
GCN. Thus, we chose melamine and phosphorous acid as
starting materials to produce the P-doped carbon nitride
in situ with special hierarchical micro-nanostructure.
[
5]
for GCN, which significantly restricts its applications. Addi-
tionally, the quantum efficiency of GCN in the visible light
region needs to be further improved. The fabrication of
hierarchical micro-nanostructures and heterogeneous ele-
ment doping for GCN are two effective methods to solve the
above problems. Typically, various kinds of micro-nanostruc-
ture GCN, including porous GCN, sphere GCN, and tubular
[
6,7]
GCN, were obtained through a hard-templating approach.
Herein, the fabrication process of phosphorus-doped
hexagonal tubular carbon nitride (P-TCN) is shown as
Scheme 1 (experimental details are given in the Supporting
Information). Simply, melamine and phosphorous acid was
dissolved in deionized water under heating. Then, under
phosphorous acid assisted hydrothermal conditions (pH 1–3),
the melamine was partly hydrolyzed in situ into cyanuric acid.
Then the regular and stable hexagonal cylinder precursors
were finally prepared through the molecule self-assembly
between melamine and cyanuric acid (for the main reactions
in the synthesis, see the Supporting Information, Scheme S1).
Simultaneously, the phosphorous acid molecules could adsorb
on the surface of precursor. After the thermal treatment, P
Nevertheless, this type of templating is time- and cost-
inefficient, for it requires environmentally hazardous reagents
[
*] S. Guo, Dr. Z. Deng, Dr. M. Li, Dr. B. Jiang, Prof. C. Tian, Prof. Q. Pan,
Prof. H. Fu
Key Laboratory of Functional Inorganic Material Chemistry, Ministry
of Education of the People’s Republic of China, Heilongjiang
University
Harbin 150080 (P.R. China)
E-mail: jiangbaojiang88@sina.com
fuhg@vip.sina.com
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201508505.
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conversion of melamine into cyanuric acid and gradual
formation of the supramolecular precursor are confirmed by
FTIR spectroscopy (Supporting Information, Figures S2, S3)
and XRD (Figures S4, S5). Meanwhile, the planar sheets
consisting of condensed tri-s-triazine units are stacked in
a perpendicular direction to the sheets via p–p interactions
(the interlayer space is 3.224 Š), the structure being exactly as
analyzed by SEM. Furthermore, the single crystal data and
structure refinement for supramolecular precursor are also
shown in the Supporting Information, Table S1. It is noted
that the elemental analysis mapping (Supporting Information,
Figure S6) show the homogeneous distribution of C, N, O and
P elements. The presence of P should be from the adsorption
of P-containing species on the supramolecular structure
because single-crystal data does not display any P-containing
species within supramolecular framework. A series of control
experiments (Supporting Information, Figures S5, S7, S8)
confirm that the reaction of melamine with cyanuric acid is
slow. Once the cyanuric acid is formed in situ, the remaining
melamine can react with cyanuric acid to form a supramolec-
ular structure rapidly owing to the strong interactions. The
phosphorous acid cannot be incorporated into the framework
because of its weak interaction with malamine; it can only
adsorb on the surface of the supramolecular structure. After
polycondensation at 5008C for 4 h, the transition from
hexagonal rod to hexagonal tube has occurred as shown in
Figure 1c,d. It is clear that tubular external morphology of
typical sample P-TCN (pH 1) is well maintained during the
polycondensation, which is distinctly different from that of
bulk GCN (Supporting Information, Figure S9b). Moreover,
the carbon nitride obtained from the pyrolysis of the
precursor that is prepared in the absence of phosphorous
also has irregular morphology (Supporting Information,
Figure S9d). These results confirm that the presence of
phosphorous acid and the slow-release of cyanuric acid by
the in situ hydrolyzation of melamine are very important for
the formation of P-TCN. The similar tubular structures are
also obtained at pH 2 or pH 3 (Supporting Information,
Figure S10). Subsequent inestigations mainly focus on the
typical sample P-TCN (pH 1). In Figure 1e,f, the TEM
measurements further confirmed that the desired hexagonal
tube is successfully obtained. Additionally, the structural
shrinkage leads to the formation of pores of 40–60 nm
embedded in the tube wall of P-TCN. It can be expected
that this micro-nanostructure will enhance the accessibility of
catalytic sites. To deepen understanding of the formation
mechanism of P-TCN, TGA-MS was conducted (Supporting
Information, Figure S11a,b). The formation of hexagonal
tubes was mainly due to the release of gas, including NH3,
NO , NO, N O/CO , PH , and P, after pyrolysis of the
Scheme 1. The formation process of phosphorus-doped tubular carbon
nitride.
from phosphorous acid squeezed into the GCN skeleton and
the P-TCN was formed. It exhibited enhanced visible-light
photocatalytic properties owing to the hierarchical micro-
nanostructure and the P doping of GCN.
As shown in SEM images, supramolecular precursors for
P-TCN (pH 1) possess a hexagonal rod structure with a length
up to 300–500 mm and a diameter of 60–100 mm (Figure 1a). A
high-magnification image (Figure 1b) reveals that the hex-
agonal rod precursors are composed of numbers of two-
2
2
2
3
Figure 1. a),b) SEM images of supramolecular precursor, c),d) SEM
images of P-TCN (PH=1), and e),f) TEM images of P-TCN (pH 1).
supramolecular complex. These results are different from
the pyrolysis of melamine (Supporting Information, Fig-
ure S12). The supramolecular precursor for carbon nitride
tube was also analyzed by the TGA-MS (Supporting Infor-
mation, Figure S11c,d). For the supramolecular precursor,
a high density of defects probably existed at the center of the
hexagonal rod because of quickly crystallizing at the early
stage of hydrothermal reaction (Supporting Information,
Figure S13). The phosphorous acid adsorbed on surface of
dimensional sheets. Then the supramolecular complex pre-
cursor was analyzed by a single-crystal X-ray diffractometer
(
Supporting Information, Figure S1). The analysis results
show that the melamine and cyanuric acid are held together
by multiple hydrogen bonds in the same plane, yielding the
[9c]
hexamer, similar to previous reports. The cyanuric acid is
from the partial in situ hydrolysis of melamine. The partial
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[
14]
precursor will also further strengthen its surface stability.
Therefore, the pyrolysis or etching of precursor starts at the
center of hexagonal rod, and gradually extends outward to
form tube-like structure. Moreover, the speculation is also
further evidenced by a series of SEM images (Supporting
Information, Figure S14).
The TGA-MS results suggest that the release of phos-
phorous species during the synthesis of P-TCN, while there is
still part of phosphorous species has been successfully
introduced into the GCN lattice, as shown in elemental
mapping images (Supporting Information, Figure S15).
During the synthesis of P-TCN, phosphorous acid plays
a key role like accelerating dissolution and hydrolysis of
melamine, and stabilizing the precursor framework because
of its acid–base interactions with melamine. Then the P
modified precursor was further condensed under 5008C
under nitrogen, resulting in the P-TCN. As XRD patterns
show (Figure 2a), the (002) peak centered at 27.78 becomes
tively. For the N 1s spectrum (Figure 2c), the small peak
located at 404.2 eV is attributed to the positive charge
localization in heterocycles; the big one starting from
396.4 eV to 402.7 eV can be deconvoluted into three peaks,
2
including 398.4 eV for sp -hybridized nitrogen in triazine
rings (CÀN=C), 400.0 eV for tertiary nitrogen N-(C) groups
3
and 400.9 eV for amino functions carrying hydrogen (CÀNÀ
H). The peak of the amino carrying N species (400.9 eV) is
found to be much higher than that in GCN (401.6 eV;
Supporting Information, Figure S17), which is attributed to
[15]
the special surface structure. Furthermore, the shift of peak
position also suggests the electron structure change for P-
TCN. The peak of P 2p binding energy is centered at 133.5 eV,
which is typical for PÀN coordination (PÀC bonding would be
1–2 eV lower), indicating that P most probably replaces C in
[16]
triazine rings to form PÀN bonds (Figure 2d). Furthermore,
31
the NMR investigations of P-TCN on the P show signals
between 10 and À20 ppm, which further prove the P doped in
[16]
framework (Supporting Information, Figure S18).
The
structure of the P-TCN sample is also confirmed by FTIR
spectra (Supporting Information, Figure S19). The sharp peak
À1
at 802 cm is caused by the breathing vibration of the triazine
[
8a]
À1
units. One new band at around 950 cm is attributed to the
[8b]
PÀN stretching mode,
implying a certain amount of P
incorporation, consistent with the EDS and XPS results.
Compared with the C element, the doped P element possesses
more electrons which will change the band structures of GCN
and improve its electric conductivity. The element content of
P is obtained from XPS analysis (Supporting Information,
Table S2) and elemental analysis (Supporting Information,
Table S3). The percentage of P from the elemental analysis is
1
.21 wt% for P-TCN (pH 1).
The optical properties and band structures of the samples
were analyzed by UV/Vis light absorption spectra and XPS
valence band spectra. The formation of hexagonal tube
increases the light absorption of P-TCN over the entire
wavelength range, which is primarily due to the multiple
reflections of incident light within the micro-nanostructure
[17]
tube (Figure 3a). The apparent color changed from pale
yellow (GCN) to brown (P-TCN) (Supporting Information,
Figure S20) is ascribed to the incorporation of P element into
GCN matrix. Moreover, an evident shift of photoabsorption
edge from 450 nm to 486 nm is observed for P-TCN. The
corresponding band gap energy decreases from 2.67 eV
(GCN) to 2.55 eV (P-TCN), which is consistent with previous
Figure 2. a) XRD patterns and b)–d) high-resolution XPS spectra of
b) C 1s, c) N 1s, and d) P 2p that are obtained from P-TCN (pH 1).
broader and weaker and shifts to slightly lower scattering
angles compared with the GCN, indicating the evident size-
[
13]
dependent properties of tube structure. The specific surface
2
À1
[8]
area of P-TCN is 22.95 m g , which is about 7 times than that
report. Then the valence band (VB) (Figure 3b) edge
2
À1
of GCN at 3.73 m g (Supporting Information, Figure S16).
P-TCN with large specific surface areas could provide more
surface active sites. With no doubt, the special micro-nano-
structure structure and introduced P heteroatom are expected
to not only change the optical and electronic band structure,
but also the charge-transfer efficiency of the GCN.
potential of P-TCN and GCN were measured by the XPS
valence band. The VB energy levels of P-TCN and GCN were
determined to be 1.44 eVand 1.67 eV, respectively. Compared
with that of GCN, the VB of P-TCN shifts by 0.23 eV
indicating that the electronic structure is altered owing to the
P doping. Apparently, the conduction band (CB) edge of
GCN and P-TCN were determined to be À1.0 eV and
À1.11 eV, respectively. The CB of P-TCN shifts to more
negative values can be attributed to the quantum confinement
effects induced by hierarchical micro-nanostructure. The
previous calculation results also show that P doping can
increase the dispersion of the contour distribution of HOMO
Further detailed electronic structures and chemical envi-
ronment of C, N, and P elements in the sample P-TCN were
analyzed with X-ray photoelectron spectroscopy (XPS)
measurements. In the C 1s spectrum (Figure 2b), the mainly
carbon species centering at 284.6 eV and 288.0 eV are
2
assigned to the graphitic carbon (CÀC) and the sp -hybridized
[18]
carbon in the N-containing aromatic ring (NÀC=N), respec-
and LUMO, which improves the carrier mobility. And this
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Figure 4. a) Time course of H evolution for GCN, TCN, and P-TCN
2
(pH 1) under visible light irradiation (l>420 nm), and b) wavelength-
Figure 3. a) UV/Vis light absorption spectra and band gap energies
dependent AQE of H evolution over 1 wt% Pt/P-TCN (left axis), UV/
2
(
(
inset), b) XPS valence band spectra, c) photoluminescence spectra
400 nm excitation at room temperature), and d) band structure align-
Vis light absorption spectra of P-TCN (right axis). c) Polarization
curves of GCN and P-TCN; d) the photoelectrochemical responses of
GCN and P-TCN under visible light irradiation.
ments of GCN and P-TCN (pH 1), respectively.
kind of electronic band structure is beneficial, for which not
only possesses the thermodynamically enhanced in photo-
catalytic reaction, but also inhibits electron–hole recombina-
tion. It is known that photoluminescence (PL) emission is
useful to disclose the efficiency of electron-hole pairs trap-
ping, migration, and transfer in semiconductor. In Figure 3c
the photoluminescence intensity of P-TCN decreased drasti-
cally, and the decreased peak intensity further confirms
a lower electron–hole recombination rate for P-TCN compar-
ing with GCN. Then the band structure alignments of GCN
and P-TCN are given in Figure 3d.
under visible-light irradiation (l > 420 nm). As presented,
the average hydrogen evolution rate of the P-TCN is
À1
67 mmolh , which is about seven times that of GCN
À1
(9 mmolh ). No hydrogen was detected in the dark test
reaction (Supporting Information, Figure S23). Meanwhile,
other P-TCN samples from different pH value and the TCN
also exhibits high photocatalytic activity, indicating hexagonal
tubes with a micro-nanostructure is beneficial for hydrogen
evolution. Furthermore, the increase of P level within P-TCN
could also improve its photocatalytic performance. The
hydrogen production reaction was allowed to proceed for
a total of 20 hours with intermittent degassing of the reaction
every 4 hours (Supporting Information, Figure S24). Under
the continuous hydrogen evolution, a total amount of
To illustrate the separation and dynamic processes of the
photogenerated charge carriers, surface photovoltage spec-
troscopy (SPV) was performed, and the results are shown in
the Supporting Information, Figure S21. Compared with
GCN, the sample P-TCN has a weak SPV response. It is
assumed that the P-TCN can easily capture photoinduced
electrons and inhibits the recombination of photogenerated
charges, which results in low surface net charges and a weak
1.339 mmol H is produced without noticeable deterioration
2
of the activity, which suggests the high stability of P-TCN
catalyst against photocorrosion. The P-TCN catalyst demon-
strates high activity for photocatalytic hydrogen evolution
based on its appropriate band alignments and unique micro-
nanostructure. Figure 4b gives the apparent quantum effi-
[
19]
SPV response. The evolution of electronic structure for P-
TCN can be further revealed by the room-temperature
electron paramagnetic resonance (EPR). A Lorentzian line
is observed for GCN and P-TCN (Supporting Information,
Figure S22), indicating the formation of unpaired electrons on
ciency (AQE) values for H evolution of the P-TCN catalyst
2
under various monochromatic light irradiation conditions. As
can be seen, the variation tendencies of AQE curves are
similar to their UV/Vis light absorption spectra. P-TCN
catalyst gives high AQE in a range of 400–450 nm and the
AQE value at 420 nm is estimated to be about 5.68%. This
better photocatalytic performance for P-TCN should be
attributed to the well-organized hexagonal tube frameworks;
moreover, P element doping narrows the band gap and
prompt the charge separation. After the photocatalytic
reaction, the catalyst was recycled and then was characterized
by XRD and FTIR, respectively (Supporting Information,
Figure S25). Indeed, there is virtually no noticeable alterna-
tion in the structure of the catalyst before and after the
reaction, again reflecting the robust nature of P-TCN.
[20]
p-conjugated CN aromatic rings. However, the Lorentzian
line for P-TCN can be greatly increased compared to the
GCN, which is presumably due to the redistribution of
electrons within P-TCN structure by the electron donation
from the phosphorus species. These characterizations illus-
trate an encouraging result that P-TCN is favored for
separation and migration of the photoinduced charge carriers,
resulting in enhanced visible-light-derived hydrogen produc-
tion performance.
Figure 4a shows a typical time course for hydrogen
production using the GCN and P-TCN (pH 1) samples
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To further illustrate the enhanced electron transfer in the
P-TCN, photoelectrochemical measurements were conducted
in a typical three-electrode cell (Figure 4c). Linear sweep
voltammetry (LSV) measurements were performed under
visible light irradiation. The observed cathodic current in the
range of À0.2 to À0.4 V versus SCE (À0.6 to À0.9 V vs. RHE)
can be ascribed to the hydrogen evolution reaction (HER).
Compared to GCN, P-TCN shows a much higher catalytic
activity. The enhanced catalytic capability was corroborated
by the photocurrent measurements. Figure 4d shows a com-
parison of the photocurrent-time curves for the above
samples with typical on–off cycles of visible light irradiation.
An enhanced photocurrent response for P-TCN is generated,
which is nearly three times higher than that of the pristine
GCN, strongly illustrating that the mobility of the photo-
excited charge carriers is promoted. Additionally, the Nyquist
plots for P-TCN catalysts exhibit low charge transfer resist-
ance as compared to those of GCN (Supporting Information,
Figure S26).
In conclusion, through phosphorous acid-assisted hydro-
thermal method, partially hydrolysis of melamine into
cyanuric acid leads to the formation of melamine–cyanuric
acid supramolecular precursor. Then the hexagonal P-TCNs
with the micro-nanostructure are obtained from supramolec-
ular precursor after thermal treatment. The hexagonal tube
with the layered stack structure significantly increases its
specific surface area; as a result, the density of active sites is
augmented. Moreover, the introduction of phosphorus
decreases the band gap energy, increases the electric con-
ductivity, and suppresses the recombination of photogener-
ated electron–hole pairs, thus improving the visible-light
photocatalytic efficiency for the hydrogen evolution in the
presence of sacrificial agents. The hexagonal carbon nitride
tube structure is also good carrier material for nanocomposite
with specified dimension and chemical functionality.
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3
Keywords: carbon nitride · micro-nanostructure · nanotubes ·
phosphorus doping · photocatalytic hydrogen evolution
2
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