A sulfur vacancy rich CdS based composite photocatalyst with g-C3N4 as a matrix derived from a Cd-S cluster assembled supramolecular network for H2 production and VOC removal

Article abstract of DOI:10.1039/c7dt04912a

By calcination, a sulfur vacancy rich CdS based composite photocatalyst with graphitic carbon nitride (g-C₃N₄) as a matrix has been synthesized successfully from a tetranuclear Cd-S cluster assembled supramolecular network. In this photocatalyst (CdS@g-C₃N₄), CdS nanoparticles with a size of about 5 to 8 nm disperse homogenously in the g-C₃N₄ matrix. During calcination, some coordinated nitrogen atoms dope in the lattice of CdS and replace sulfur atoms, which generates a large number of sulfur vacancies. Under visible light irradiation, CdS@g-C₃N₄ exhibits excellent H₂ production activity with a rate achieving as high as 19.88 mmol g^-1 h^-1 in the absence of a Pt cocatalyst. Its H₂ production ability remains stable for 30 h, which does not decay. Besides H₂ production, CdS@g-C₃N₄ also shows excellent photocatalytic activity for Volatile Organic Compound (VOC) degradation. For a photocatalyst, chemical content plays an important role in its performance. Here, the influence of sulfur vacancies on H₂ production and VOC degradation is discussed in detail. We expect that the sulfur vacancy rich CdS@g-C₃N₄ can act as an efficient material for H₂ production and indoor air purification.

Full text of DOI:10.1039/c7dt04912a

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PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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Sulfur vacancies rich CdS based composite photocatalyst with g-C3N4
as matrix derived from Cd-S cluster assembled supramolecular
Received 00th January 20xx,
Accepted 00th January 20xx
network for H2 production and VOCs removal
DOI: 10.1039/x0xx00000x
Yaqin Wang, Xinxin Xu*, Wei Lu, Yuqiu Huo* and Lijun Bian*
www.rsc.org/
By calcination, sulfur vacancies rich CdS based composite photocatalyst with graphitic carbon nitride (g-C3N4) as matrix has
been synthesized successfully from tetranuclear Cd-S cluster assembled supramolecular network. In this photocatalyst
(CdS@g-C3N4), CdS nanoparticles with the size about 5 to 8 nm disperse homogenously in g-C3N4 matrix. During
calcination, some coordinated nitrogen atoms dope in the lattice of CdS and replace sulfur atoms, which generates a large
number of sulfur vacancies. Under visible light irradiation, CdS@g-C3N4 exhibits very excellent H2 production activity with
the rate achieving as high as 19.88 mmol·g-1·h-1 without the existence of Pt cocatalyst. Its H2 production ability keeps stable
for 30 h, which does not decay. Besides H2 production, CdS@g-C3N4 also shows excellent photocatalytic activity for Volatile
Organic Compounds (VOCs) degradation. For a photocatalyst, chemical content plays an important role in its performance.
Here, the influence of sulfur vacancies on H2 production and VOCs degradation is discussed in detail. We expect the sulfur
vacancies rich CdS@g-C3N4 can act as an efficient material for H2 production and indoor air purification.
Introduction
and g-C3N4.38,39 In these methods, photocatalysts are formed
through self-assemble or precipitation of CdS particle on g-C3N4. But
Nowadays, with exhaustion of oil, natural gas and coal, global
concern over energy crisis has urged great effort to explore clean
and sustainable energy.1-3 H2 is considered as an ideal substitute for
traditional fossil fuels, due to its high efficiency and eco-
the random growth process leads to some serious consequences,
such as overgrowth or aggregation of CdS particle, as well as its
inhomogeneous distribution on g-C3N4.40,41 Anyone of these
problems can decrease separation efficiency of photogenerated
electron-hole pairs and lead to fatal influence on H2 production
activity.
friendliness.4-6 Photocatalytic water splitting is
a prospective
technique to obtain H2.7-9 As a visible light active photocatalyst,
graphitic carbon nitride (g-C3N4) has attracted more and more
attentions.10-12 Its narrow band gap (Eg = 2.7 eV) facilitates visible
light absorption, simultaneously, the negative conductive band
energy (Ecb = -1.0 V vs. NHE) offers sufficient overpotential for H2
production.13-18 The prospect of g-C3N4 looks promising, but its H2
production activity is weakened in great extent due to quick
recombination of photogenerated electron-hole pairs.19-33 For g-
C3N4, to enhance H2 production rate, the construction of composite
material with CdS is a feasible strategy, because their matched band
structures facilitates the generation of heterojuction, which
promotes the separation of photogenerated electron-hole pairs.34-37
Up to now, several experimental methods, such as hydrothermal,
solvothermal, chemical impregnation and self-transformation have
been applied to synthesis composite photocatalysts based on CdS
Scheme
1 Structure and formation process of CdS@g-C3N4
composite material with SN as precursor.
To break above bottleneck, a unique strategy, which facilitates
the generation of CdS nanoparticles with small size and their
uniform distribution in g-C3N4 matrix, is necessary. In this aspect,
supramolecular network assembled by Cd-S polynuclear cluster
inspires us greatly, because it can be employed to fabricate CdS
based composite photocatalysis with g-C3N4 as matrix directly
through calcination.42,43 Moreover, compared with other
precursors, Cd-S polynuclear cluster assembled supramolecular
network also possesses some peculiar advantages. At first, in
supramolecular network, Cd-S polynuclear cluster are connected
Department of Chemistry, College of Science, Northeast University, Shenyang,
110819, P.R. China. E-mail: xuxx@mail.neu.edu.cn (Prof. Xinxin. Xu); Fax: 086-
024-83684533; (Prof. Xinxin Xu); huoyuqiu@mail.neu.edu.cn (Prof. Yuqiu Huo)
bianlijun@mail.neu.edu.cn (Prof. Lijun Bian).
Supporting information for this article is given via a link at the end of the docum:
SEM of NSN; XPS Cd 3d and S 2p of CdS@g-C3N4; Mechanism of photocatalytic H2
production; Time courses of photocatalytic benzene degradation and CO2 production;
repeated time courses of benzene degradation. CIF file of SN.
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with high order, so, after calcination, obtained CdS particles are Teflon-lined stainless steel bomb and kept at 120 ˚C under
embedded in g-C3N4 evenly.44-46 Secondly, during calcination, CdS is autogenously pressure for 96 h. A large amount of yellow crystals of
surrounded by organic ligands tightly, which restricts its overgrowth SN were obtained. Crystals of SN were ground for 2 h with an agate
and produces CdS with small dimension.47-49 Furthermore, mortar and pestle. The resulted powders were dissolved in
coordinated nitrogen atoms can dope in the lattice of CdS and methanol and placed in a Teflon autoclave, which were heated in a
replace the sites of sulfur atoms after calcination which produces microwave oven at 180 W for 2 h. The nanoparticle of SN (NSN) was
sulfur vacancies. This is benefit for the improvement of separated by centrifugation, rinsed with water, and then dried in a
photocatalytic activity, because sulfur vacancies not only narrow vacuum drier at 80 ˚C for 24 h.
the band gap of a photocatalyst, but also promote the separation of
Synthesis of CdS@g-C3N4 composite photocatalyst
photogenerated electron-hole pairs.50-54 So we envisage, with Cd-S
polynuclear cluster assembled supramolecular network as
precursor, after calcination, an efficient sulfur vacancies rich
composite photocatalyst constructed by CdS and g-C3N4 can be
obtained.
The powders of NSN were put in a tube furnace and heated at the
rate of 3 ˚C·min-1 to 550 ˚C under the protection Ar gas flow. The
samples were kept at 550 ˚C for 2 h and subsequently cooled to the
room temperature. The obtained powders were collected, washed
with water for several times and then dried in a vacuum oven at 70
˚C for 10 h. The product was denoted as CdS@g-C3N4(A). The
composite photocatalysts obtained after heated for 4 and 6 h were
donated as CdS@g-C3N4(B) and CdS@g-C3N4(C) respectively.
Our assumption is proven to be feasible by successful fabrication
of CdS@g-C3N4, a sulfur vacancies rich CdS based composite
photocatalyst with g-C3N4 as matrix. This photocatalyst was
obtained from Cd4(DMMPY)8(H2O)2·2(H2O) (SN) (DMMPY = 4,6-
Dimethyl-2-mercaptopyrimidine),
a 3D supramolecular network
Electrochemical measurements
assembled by tetranuclear Cd-S cluster (Scheme 1). In CdS@g-C3N4,
CdS particles with the size about 5 to 8 nm disperse evenly in g-C3N4
matrix. Photocatalytic water splitting experiment illustrates CdS@g-
C3N4 exhibits outstanding H2 production property under visible light
irradiation. No obvious decrease in H2 production rate occurs during
water splitting process for 30 h. Besides H2 production, its
photocatalytic activity also takes effect on Volatile Organic
Compounds (VOCs) degradation, such as acetaldehyde and
benzene. Furthermore, we also discussed the influence of sulfur
vacancy on H2 production and VOCs removal activity.
To prepare the electrode, CdS@g-C3N4 (10 mg) was dispersed
into 5 mL ethanol to give homogeneous suspension upon bath
sonication. The suspension (5 μL) was dip-coated onto FTO and the
electrode
was
then
dried
at
room
temperature.
Photoelectrochemical tests were carried out with a conventional
three-electrode system in quartz cell filled with 0.1 M Na2SO4
electrolyte (40 mL), with the CdS@NC/FTO electrode serving as the
working electrode, a Pt plate as the counter electrode, and a
saturated calomel electrode (SCE) as the reference electrode. A 300
W Xe lamp (Bejing Perfect Co. Ltd., PLS-SXE-300UV) with a cutoff
filter (λ ≥ 420 nm) was used as the excitation light source for visible
irradiation. Electrochemical impedance spectra (EIS) were recorded
in potentiostatic mode. The amplitude of sinusoidal wave was 10
mV, and the frequency of the sinusoidal wave ranged from 100 kHz
to 0.05 Hz.
Experimental section
Materials and methods
All purchased chemicals were of reagent grade and used without
further purification. PXRD patterns were recorded on X-ray
diffractometer with CuKR (λ=1.5418 Å) radiation (Philips X’Pert Pro
Super, Philips). The Fourier transform infrared (FTIR) spectra were
recorded on a FTIR spectrometer (Nicolet 6700). The electron
paramagnetic resonance spectrum (EPR) was carried out using an
Endorspectrometer (JEOL ES-ED3X). The morphology was observed
on an ultra plus field emission scanning electron microscope (SEM,
ultra plus, Zeiss) and a transmission electron microscopy (TEM,
JEOL, JEM-2100F). XPS was performed with MgKα radiation (1253.6
eV) as an excitation source (ESCALab MKII, Thermo Scientific and
Waltham, MA). The Brunauer-Emmett-Teller (BET) surface area and
porous structure were measured from nitrogen adsorption and
Photocatalytic H2 production
The photocatalytic reactions were conducted in a 100 mL quartz
reactor at room temperature and the visible light source is 8 cm
away from this reactor. Catalyst (30 mg) was dispersed in 60 mL
lactic acid (10 %, as sacrificial agent) solution with stirring. At first,
the system was deaerated by bubbling N2 for 20 min, then
irradiated by a 300 W Xe lamp (Bejing Perfect Co. Ltd., PLS-SXE-300
UV) equipped with an cut off filter (λ ≥ 420 nm). The generated H2
were measured through the online gas chromatograph (GC 7900)
equipped with a TCD detector.
The apparent quantum yield (AQY) was measured using the same
light source equipped with a monochromatic filter (450 nm). The
desorption isotherms at 77
K (ASAP 2020, Micromeritics,
Instrument Corp). Diffuse reflectance spectra (DRS) were recorded
on a Shimadzu-2501PC spectrometer using BaSO4 as a standard.
Photoluminescence (PL) spectra were recorded by FLSP920
fluorescence spectrometer. Electrochemical experiments were
conducted on CHI 660E electrochemical workstation.
photo flux of the light was determined with
a radiometer
(Photoelectric instrument factory of Beijing normal university). The
apparent quantum yield was calculated using the following
equation.
AQY (%) = (number of reacted electrons/number of incident
photons) × 100 % = (2 × number of evolved H2 molecules/number of
incident photons) × 100 %
Synthesis of Cd4(DMMPY)8(H2O)2·2(H2O) (SN) and its nanoparticle
(NSN)
At first, Cd(OAc)·2H2O (0.027 g, 0.1 mmol) was solved in 8 mL
ethanol. DMMPY (0.028 g, 0.2 mmol) was added in to above
solution. Then, its pH value was adjusted to 4.0 with KOH and
stirred for 15 min. Finally, the mixture was transferred to a 20 mL
Photocatalytic degradation of VOCs
Photocatalytic degradation of VOCs was studied in a 2.0 L quartz
reactor. The reactor was filled with O2/N2 (20 %) at first. Then liquid
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acetaldehyde (or benzene) and water were injected into the reactor symmetry-related atoms (Cd1A, Cd2A generated by the symmetry
and vaporized into gas phase. Finally, CdS@g-C3N4 (30 mg) was operation -x, -y+2, -z) are linked and form an interesting
fixed in the reactor. Above mentioned light source was used. Before tetranuclear Cd cluster (Fig. 1a). Finally, adjacent clusters are
reaction, the sample was kept in dark for 90 min to reach connected and form three-dimensional supramolecular network
adsorption/desorption equilibrium. The concentrations of VOCs and with intensive hydrogen bonds and π-π interactions (Fig. 1b). The
resulted CO2 were analyzed by a gas chromatograph (GC7900 morphology of NSN was studied with SEM, which exhibits spherical
equipped with a flame ionization detector and methane reforming appearance with diameter about 50 to 80 nm (Fig. S1, ESI).
furnace). Initial concentration of VOCs was 100 ppm and relative
humidity (R. H.) level was kept at 40 %. The degradation rate of
VOCs was calculated by the equation of (1-c/c0) %, in which c0
represents initial concentration and c is the concentration at
intervals. CO2 conversion rate was obtained by the equation of
(cCO2/ctotal) %; in which cCO2 is the concentration of CO2 and ctotal
represents theoretic CO2 concentration produced by VOCs.
To study the kinetic process of this reduction reaction, a set of
apparent rate constants (k) were obtained with constant relative
humidity (40 %) while varying concentration of VOCs. The
Fig. 1 (a) The fundamental unit of SN; (b) 3D supramolecular
concentrations of VOCs were 60, 80, 100, 120, 140 and 160 ppm.
network of SN.
Based on above data, the curve of k versus concentration of VOCs
was drawn. Langmuir-Hinshelwood model (1) was employed to fit
these curve to obtain the adsorption constants of VOCs (KVOCs) and
H2O (Kwater). In this equation, k represents the surface rate constant;
S is the surface area; n and m are the Freundlich exponents.
k = k×S×KnVOCs(VOCs)n-1(Kwater[H2O])m/{1 + (KVOCs[VOCs])n +
(Kwater[H2O])m}2 (1)
X-Ray crystallography
Suitable single crystal of SN was carefully selected under an optical
microscope and glued on a glass fiber. Structural measurement was
performed on a Bruker AXS SMART APEX II CCD diffractometer at
293 K. The structure was solved with the direct method and refined
by the full-matrix least-squares method on F2 using the SHELXTL 97
crystallographic software package. Anisotropic thermal parameters
were used to refine all non-hydrogen atoms. Carbon-bound
hydrogen atoms were placed in geometrically calculated positions;
Oxygen-bound hydrogen atoms were located in the difference
Fourier maps, kept in that position and refined with isotropic
temperature factors. The details have been deposited to the
Fig. 2 (a) PXRD of CdS@g-C3N4; (b) FTIR spectra of CdS@g-C3N4; (c)
Solid-state 13C NMR spectra of CdS@g-C3N4; (d) EPR spectra of
CdS@g-C3N4, CdS and g-C3N4.
Cambridge Crystallographic Data Centre (CCDC 1576002).
Results and discussion
Structure, morphology and characterization
CdS@g-C3N4 composite photocatalysts were obtained through
the calcination of NSN. PXRD was applied to study their structures.
The samples exhibit intense diffractions at 25.1˚, 26.5˚, 28.1˚, 36.4˚,
43.9˚, 47.8˚, 52.1˚, 66.8˚, 71.1˚ and 75.5˚. Based on JCPDS card (No.
41-1049), these peaks can be attributed to the (100), (002), (101),
(102), (110), (103), (112), (203), (211) and (105) planes of CdS
respectively (Fig. 2a).55 In PXRD, the diffractions belonging to g-C3N4
disappear, to identify its existence, FTIR was employed. The peaks
at 1622, 1408, 1319 and 1238 cm-1 can be ascribed to characteristic
bands of CN heterocycle, while the signal at 808 cm-1 originates
from s-triazine ring (Fig. 2b). All these facts illustrate formation of g-
C3N4 after calcination of NSN. This result is further confirmed by
solid-state 13C NMR spectra. All the CdS@g-C3N4 composite
photocatalysts exhibit two signals at 156.2 and 164.1 ppm. These
can be attributed to carbon atoms of melem (CN3) and CN2(NH2),
which suggests the generation of poly(tri-s-triazine) structure in g-
Single crystallographic X-ray diffraction analysis illustrates there
exist two independent Cd atoms in the fundamental unit of SN.
Cd(1) connects with four sulfur atoms from different DMMPY
ligands, with Cd-S bond distances range from 2.624 to 2.723 Å. The
other two coordination sites are occupied by two nitrogen atoms
with bond distance 2.416 and 2.450 Å respectively. This results in
the distorted octahedron coordination mode of Cd(1). Cd(2) adopts
the similar coordination mode with Cd(1), which connects with
three sulfur atoms (with bond distance 2.601 to 2.752 Å) and two
nitrogen atoms (with bond distance 2.402 and 2.442
Å
respectively). In Cd(2), the last site is occupied by water molecule
and the Cd-O distance is 2.274 Å. The DMMPY ligand adopts two
kinds of connection mode, one is chelating, the other is bridging.
With these two coordination modes, Cd(1), Cd(2) and their
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C3N4 (Fig. 2c). As an effective method to investigate the defects in a calcination, the resulted CdS particles are embedded in g-C3N4
solid material, EPR can provide sensitive and direct structural matrix homogeneously.
information. Here, to confirm the existence of sulfur vacancies in
X-ray photoelectron spectroscopy (XPS) was employed to study
CdS@g-C3N4, EPR spectrum was employed (Fig. 2d). The signals of the composition and surface electronic state of CdS@g-C3N4
CdS and g-C3N4 are in active. All these CdS@g-C3N4 composite composite photocatalysts. Wide-scan XPS spectrum exhibits
photocatalysts exhibit resonance signal at g = 2.004. From CdS@g- obvious signals of S 2p, C 1s, N 1s and Cd 3d at 162.7, 284.9, 400.6
C3N4(A) to CdS@g-C3N4(C), the N/C ratio range from 1.561 to 1.564, and 405.1, 411.8 eV (Fig. 4a to 4c). Although these composite
which is equal to pristine g-C3N4. This suggests N defects do not photocatalys are obtained under different conditions, their
exist in g-C3N4 and the EPR signal originates from S vacancies.56,57 elemental distributions are nearly similar (Table 1). Further
Furthermore, from CdS@g-C3N4(A) to CdS@g-C3N4(C), the peak exploration illustrates, high-resolution Cd 3d spectra can be
intensity of EPR signal decreases obviously and CdS@g-C3N4(A) separated into two peaks at 405.1 and 411.8 eV, which can be
shows the highest EPR signal in these composite photocatalysts. ascribed to Cd 3d5/2 and Cd 3d3/2 respectively (Fig. S3, ESI).59,60 For S
This result illustrates CdS@g-C3N4(A) possesses more sulfur 2p, two peaks appear at 161.1 and 162.4 eV corresponds to S 2p3/2
vacancies than CdS@g-C3N4(B) and CdS@g-C3N4(C). It has been and S 2p1/2 (Fig. S4, ESI). All the results illustrate CdS has been
confirmed that sulfur vacancy play an important role for formed in these samples successfully.61,62
enhancement of photocatalytic activity.
Fig. 3 TEM images of (a) CdS@g-C3N4(A); (b) CdS@g-C3N4(B) and (c)
CdS@g-C3N4(C); HRTEM images of (d) CdS@g-C3N4(A); (e) CdS@g-
C3N4(B) and (f) CdS@g-C3N4(C).
Table 1 The element contents of CdS@g-C3N4 photocatalysts.
CdS@g-C3N4
Cd (%)
A
B
C
6.2
6.4
6.5
S (%)
6.1
6.3
6.4
C (%)
N (%)
34.2
53.5
18.5
53.2
28.3
34.1
53.2
13.5
54.6
31.9
34.0
53.1
10.2
54.1
35.7
Fig. 4 XPS survey of (a) CdS@g-C3N4(A); (b) CdS@g-C3N4(B) and (c)
CdS@g-C3N4(C); High resolution C 1s spectra of (d) CdS@g-C3N4(A);
(e) CdS@g-C3N4(B) and (f) CdS@g-C3N4(C); High resolution N 1s
spectra of (g) CdS@g-C3N4(A); (h) CdS@g-C3N4(B) and (i) CdS@g-
C3N4(C).
N-Cd
C=N-C (%)
N-(C)3 (%)
The morphology of CdS@g-C3N4 was studied with TEM. CdS@g-
C3N4 shows similar appearance and dimension with NSN (Fig. 3a to
As for C 1s, there exist two states after deconvolution of high-
resolution spectra centering at 288.2 and 284.6 eV, which originates
from sp2 hybridized carbon of aromatic ring and sp2 C-N (or
graphitic carbon). These peaks are characteristic features of g-C3N4
(Fig. 4d to 4f).63,64 N 1s XPS spectra reveal coexistence of three kinds
nitrogen atoms, which appears at 396.6, 397.9 and 399.5
respectively (Fig. 4g to 4i).65,66 The peak at 397.9 eV corresponds to
sp2-hybridized N atom, which formed by one single bond with one
carbon atom and one double bond with two carbon atoms (C=N-C)
in triazine rings. While the peak locating at 399.5 eV can be ascribed
to tertiary N species (N-(C)3). These peaks are in consistence with
recently reported g-C3N4 based composite materials. The peak
locating at 396.6 eV is the characteristic N 1s signal of Cd-N bond,
which suggests in the lattice of CdS, some sulfur atoms are replaced
by nitrogen and generates new Cd-N bonds. Based on results of EPR
and XPS, we can conclude nitrogen atoms have doped in the lattice
of CdS successfully, which produces sulfur vacancies. Unlike other
element, such as Cd, S and C, whose content has nothing to do with
3c). Furthermore, in CdS@g-C3N4,
a lot of spherical shaped
nanoparticles with size 5 to 8 nm distribute uniformly. The
homogenous distribution of CdS in g-C3N4 was also confirmed by
element mapping (Fig. S2, ESI). High resolution TEM images suggest
lattice plane distance of these particle is 0.35 nm, which is in good
agreement with the (110) plane of CdS (Fig. 3d to 3f).58 Besides the
lattice spacing of 0.35 nm belonging to CdS, a different kind of
lattice fringes with spacing of 0.326 nm can be found, which
corresponds to the typical (002) interlayer-stacking distance of g-
C3N4. This suggests after calcination, DMMPY ligand converts to g-
C3N4 successfully. For CdS@g-C3N4, its unique structure originates
from two aspects. At firstly, in tetranuclear Cd-S cluster, Cd(II) ions
are surrounded tightly by adjacent DMMPY ligands, which limits its
overgrowth and generates CdS particles with small size. Secondly, in
supramolecular network, neighboring tetranulcear Cd-S clusters are
connected through π-π interactions with high order, so, after
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calcination time; it can be observed clearly the content of nitrogen photocatalysts. This is benefit for the enhancement of H2
species is influenced greatly by reaction time.
production activity.
The specific surface area and porous nature of CdS@g-C3N4
Electrochemical methods are powerful tools to investigate
composite photocatalysts were studied with Brunauer-Emmett- interfacial electron production and charge transportation on
Teller (BET) method. The N2 adsorption/desorption isotherms photocatalysts. Here, the separation of electron-hole pair was
belonging to type-IV isotherm with a large slope at higher relative studied with photocurrent spectra at first. For CdS@g-C3N4
pressure, which is typical character of mesoporous materials (Fig. composite photocatalysts, after irradiated with visible light, the
5a to 5c). From CdS@g-C3N4(A) to CdS@g-C3N4(C), their BET specific photocurrent produces at once and then reaches the maximum
surface areas are 112.8, 118.9 and 116.8 m2/g. The pore-size value. If the light is shut off, the photocurrent disappears quickly
distribution of CdS@g-C3N4 composite photocatalysts are calculated (Fig. 6c). CdS@g-C3N4(A) exhibits more intensive photocurrent than
from the above isotherms with the BJH model. The results CdS@g-C3N4(B) and CdS@g-C3N4(C), which suggests in CdS@g-
demonstrate the size of their pores range from 2 to 15 nm (Fig. 5d). C3N4(A), the photogenerated electron-hole pair can be separated
Their average pore sizes are 6.3, 5.4 and 5.9 nm, respectively.
quickly. To discuss charge transportation process in detail, EIS was
used (Fig. 6d). In these composite materials, CdS@g-C3N4(A) has the
smallest arc radius, and this implies the effective separation of
electron-hole pair happens on its interfaces. Based on optical and
electrochemical results, we can conclude CdS@g-C3N4(A) exhibits
more excellent photogenerated electron-hole pair separation
property than the other two composite photocatalysts.
Fig. 5 N2 adsorption/desorption isotherms of (a) CdS@g-C3N4(A); (b)
CdS@g-C3N4(B) and (c) CdS@g-C3N4(C); (d) The BJH mesoporous
size distribution of CdS@g-C3N4.
Optical and electrochemical analysis
Diffuse reflectance spectra (DRS) of CdS@g-C3N4 composite
photocatalysts were studied and their band gaps were calculated
with Tauc equation. From CdS@g-C3N4(A) to CdS@g-C3N4(C), their
absorption edges appear at 592, 579 and 552 nm corresponding to
band gap energy of 2.09, 2.14 and 2.25 eV respectively (Fig. 6a). For
pure CdS and g-C3N4, their absorption edges locate at 520 and 461
nm with band gap 2.40 and 2.68 eV. Red-shifts of absorption edges
illustrate CdS@g-C3N4 composite photocatalysts exhibit more
intensive light adsorption ability than pure CdS and g-C3N4.
Furthermore, in composite photocatalysts, CdS@g-C3N4(A) exhibits
the narrowest band gap, which illustrates its photo adsorption
region is broader than CdS@g-C3N4(B) and CdS@g-C3N4(C).
Photoluminescence spectrum was applied to study the separation
of photogenerated electron-hole pair. For CdS@g-C3N4 composite
photocatalysts, with excitation at 400 nm, their main emission
peaks appear at 468 nm (Fig. 6b). As we all known, in
photoluminescence spectra, emission intensity is inversely
proportional to separation efficiency of photogenerated electron-
hole pair. So the weak emission intensity suggests high separation
rate of electron-hole pair. Here, CdS@g-C3N4(A) exhibits the lowest
photoluminescence intensity, and this implies its electron-hole pair
separation efficiency is higher than the other two composite
Fig. 6 (a) DRS of CdS@g-C3N4; (b) Photoluminescence spectra of
CdS@g-C3N4; (c) Photocurrent spectra of CdS@g-C3N4; (d) ESI of
CdS@g-C3N4.
Photocatalytic H2 production
Under visible light irradiation, all these CdS@g-C3N4 composite
materials exhibit excellent photocatalytic H2 production activities
(Fig. 7a). From CdS@g-C3N4(A) to CdS@g-C3N4(C), their H2
production rates are 19.88, 13.76 and 7.58 mmol·h-1·g-1, with
apparent quantum yield (AQY) 16.22, 11.26 and 6.19 % respectively
(Fig. 7b). Compared with other g-C3N4 based composite
photocatalysts, H2 production rate of CdS@g-C3N4 is enhanced in
great extent, which can be ascribed to the effect of sulfur vacancy
(Table 2). Furthermore, it can also be observed clearly calcination
time exhibits great influence on H2 production rate. With its
prolonging, H2 production rate decreases gradually. To explain this
phenomenon, the exploration of photocatalytic mechanism is
essential. For CdS@g-C3N4, its photocatalytic mechanism is similar
with other photocatalysts constructed by CdS and g-C3N4. Under
visible light irradiation, CdS and g-C3N4 are both excited, the
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photogenerated holes shifts from valence band of CdS to g-C3N4, at concentration of acetaldehyde keeps stable. This illustrates merely
the same time, photogenerated electrons move from conductive visible light is inactive for its degradation. In sharp contrast,
band of g-C3N4 to CdS (Fig. S5, ESI). This can lead to the separation addition of CdS@g-C3N4 leads to obvious decreasing of
of electron-hole pairs and enhancement of photocatalytic activity. acetaldehyde. After visible light illumination for 120 min, about
So, in CdS@g-C3N4 composite photocatalyst, electron conductivity is 95.2, 83.1 and 73.5 % of acetaldehyde are degraded by CdS@g-
a significant factor which influences separation of electron-hole pair C3N4(A), CdS@g-C3N4(B) and CdS@g-C3N4(C), with degradation rate
and H2 production rate.
constants 0.024, 0.014 and 0.010 min-1 respectively (Fig. 8a). The
degradation of acetaldehyde is accompanied with the increasing of
CO2, which suggests acetaldehyde has converted to CO2
successfully. From CdS@g-C3N4(A) to CdS@g-C3N4(C), CO2
conversion rates achieve at 92.1 %, 80.1 % and 72.9 % (Fig. 8b).
Based on acetaldehyde degradation efficiency and CO2 conversion
rate, we can conclude, CdS@g-C3N4(A) exhibits more excellent
acetaldehyde degradation ability than CdS@g-C3N4(B) and CdS@g-
C3N4(C).
Fig. 7 (a) Time courses of photocatalytic H2 production; (b) The
average rate of H2 production; (c) Repeated time courses of H2
production for CdS@g-C3N4(A); (d) PXRD of CdS@g-C3N4(A) before
and after H2 production.
Fig. 8 (a) Time courses of photocatalytic acetaldehyde degradation;
(b) The rate of CO2 production; (c) The connection between k and
concentration of acetaldehyde; (d) The mechanism of acetaldehyde
degradation; (e) Repeated time courses of acetaldehyde
degradation.
To our knowledge, electron conductivity is determined by
morphology, dimension, surface area and chemical composition.
But in CdS@g-C3N4, similarity of the first three parameters suggests
they are not decisive factors responsible for difference in H2
production rate. Here, as revealed by EPR, the most obvious
discrepancy in these photocatalysts is chemical composition, in
detail, is the concentration of sulfur vacancies. From CdS@g-
C3N4(A) to CdS@g-C3N4(C), the concentration of sulfur vacancy
decreases obviously, accompanied with the reduction of H2
production rate. As an excellent electron conductor, sulfur vacancy
can move photogenerated electrons in time and impedes its
recombination with holes. So, it’s decreasing shut down electron
transportation ability and H2 production rate. This is in agreement
with the results of optical and electrochemical analysis. For CdS@g-
C3N4(A), its durability and stability are significant factors to evaluate
its prospect in practical applications. Here, H2 production
experiment of CdS@g-C3N4(A) is repeated five times, but its H2
production rate still keeps at high level (Fig. 7c). Furthermore,
recycled CdS@g-C3N4(A) exhibits identical PXRD patterns with
original sample, which suggests the structure is well retained (Fig.
7d). All these facts imply CdS@g-C3N4(A) can be employed as an
efficient and stable photocatalyst for H2 production.
To analyze the superiority of CdS@g-C3N4(A) over the other two
photocatalysts, the exploration of mechanism is necessary. The
curve of rate constants versus concentration of acetaldehyde was
obtained when the relative humidity was set as a constant while the
concentration of acetaldehyde was varied (Fig. 8c). Langmuir-
Hinshelwood model was used to fit these curves and the good
correlations (R2 > 0.99) illustrate it is feasible for above three
photocatalysts. Based on Langmuir-Hinshelwood theory, the
degradation of acetaldehyde completes three steps: at first, oxygen
atoms from acetaldehyde and H2O were captured by sulfur
vacancies from CdS@g-C3N4 and fastened on its surface; secondly,
positive holes on valence band of C3N4 react with surface bound
H2O to produce hydroxyl radical (·OH), the negative electrons on
conduction band of CdS is taken by O2 and generate super oxide
radical (O2·-); finally, hydroxyl radical (·OH) and super oxide radical
(O2·-) react with acetaldehyde, which lead to its oxidization and
degradation (Fig. 8d). In this process, besides acts as electron
carrier, sulfur vacancy also serves as acetaldehyde trapper, which
captures, fastens acetaldehyde and accelerates its degradation.
Compared with the other two photocatalysts, CdS@g-C3N4(A)
possesses more sulfur vacancies, which prompts the improvement
of its acetaldehyde degradation ability.
Photocatalytic degradation of VOCs
For a photocatalyst, stability and universality are significant
factors for its practical application. To evaluate the recyclability of
CdS@g-C3N4(A), 5 successive cycles of acetaldehyde degradation
reactions were carried out and CdS@g-C3N4(A) still shows excellent
For CdS@g-C3N4, to study its VOCs degradation activity,
acetaldehyde was chosen as a probe and its degradation was
conducted under visible light. In absence of CdS@g-C3N4, the
6 | J. Name., 2012, 00, 1-3
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removal property with its efficiency remains about 95 % (Fig. 8e). This work was supported by National Natural Science Foundation of
All these facts suggest that CdS@g-C3N4(A) can act as a high China (21303010) and Opening Project of Key Laboratory of
efficient and stable photocatalyst to remove acetaldehyde from air. Polyoxometalate Science of Ministry of Education (130028720).
To study the universality of CdS@g-C3N4(A) for VOCs removal,
another typical pollutant, benzene was chosen as a model. In 120
Notes and references
min, about 85.2 % benzene is degraded and CO2 conversion rate
achieves as high as 90.6 % (Fig. S6, ESI). More importantly, its
photocatalytic activity does not show any loss after 5 cycle
reactions (Fig. S7, ESI). All these results illustrate CdS@g-C3N4(A) is
an efficient and stable photocatalyst for the degradation of VOCs in
the air.
1 J. Willkomm, K. L. Orchard, A. Reynal, E. Pastor, J. R. Durrantc, E.
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2
M. A. Nasalevich, R. Becker, E. V. Ramos-Fernandez, S.
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Table 2 Comparison of photocatalytic H2 production rate reported
in the literature with sulfur vacancies rich CdS@g-C3N4 in our work.
4 R. S. Khnayzer, V. S. Thoi, M. Nippe, A. E. King, J. W. Jurss, K. A. El
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Photocatalyst
CdS@g-C3N4
Zn0.2Cd0.8S@g-C3N4
CdS@g-C3N4
Production rate
4.49 mmol·g-1·h-1
4.16 mmol·g-1·h-1
30.2 mmol·g-1·h-1
12.5 mmol·g-1·h-1
5.98 mmol·g-1·h-1
0.12 mmol·g-1·h-1
2.56 mmol·g-1·h-1
3.63 mmol·g-1·h-1
4.15 mmol·g-1·h-1
2.56 mmol·g-1·h-1
0.68 mmol·g-1·h-1
0.25 mmol·g-1·h-1
0.22 mmol·g-1·h-1
2.62 mmol·g-1·h-1
0.99 mmol·g-1·h-1
0.02 mmol·g-1·h-1
0.04 mmol·g-1·h-1
0.21 mmol·g-1·h-1
0.11 mmol·g-1·h-1
0.91 mmol·g-1·h-1
Pt
Ref
34
35
36
37
39
40
41
50
55
56
60
62
19
21
22
23
26
27
28
29
Here
yes
no
yes
no
no
no
no
no
yes
no
no
no
no
no
no
no
no
no
no
no
5 Y. J. Cao, S. Chen, Q. Q. Luo, H. Yan, Y. Lin, W. Liu, L. L. Cao, J. L. Lu,
J. L. Yang, T. Yao, S. Q. Wei, Angew. Chem. Int. Ed. 2017, 56, 12191-
12196.
CdS@g-C3N4
CdLa2S4@g-C3N4
CdS·Ni(OH)2@g-C3N4
CdS·NiS@g-C3N4
ZnIn2S4@g-C3N4
CdS@g-C3N4
6 W. W. Zhao, Y. Huang, Y. Liu, L. M. Cao, F. Zhang,Y. M. Guo, B.
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CdS·NiS@g-C3N4
CdS@g-C3N4
NiS@g-C3N4
AgS@g-C3N4
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MoS2@g-C3N4
NiS@g-C3N4
NiS@g-C3N4
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WS2@g-C3N4
ZnS@g-C3N4
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WS2@g-C3N4
ZnIn2S4@g-C3N4
CdS@g-C3N4
19.88 mmol·g-1·h- no
Conclusion
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In conclusion, with Cd-S cluster assembled supramolecular
network as precursor, a new strategy has been explored to obtain
sulfur vacancies rich composite photocatalyst composed by CdS and
g-C3N4. Based on this method, an effective photocatalyst, CdS@g-
C3N4 has been synthesized, in which CdS particles with the size
about 5 to 8 nm distribute evenly in g-C3N4 matrix. Compared with
other analogues, CdS@g-C3N4 exhibits more excellent H2
production activity with H2 production rate achieves at 19.88
mmol·g-1·h-1. The stability of CdS@g-C3N4 is very outstanding, after
several successive cycles of H2 production reactions, its H2
production rate still retains at high level. In addition, CdS@g-C3N4
also exhibits superior photocatalytic activity for VOCs degradation.
The advantages of CdS@g-C3N4 in H2 production and VOCs
degradation can be attributed to existence of sulfur vacancy, which
makes it becomes a promising material for H2 energy development
as well as an ideal tool to remove VOCs contaminants from air.
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Table of Contents Entry
Sulfur vacancies rich CdS based composite photocatalyst with g-C3N4 as
matrix derived from Cd-S cluster assembled supramolecular network
for H2 production and VOCs removal
Yaqin Wang, Xinxin Xu*, Wei Lu, Yuqiu Huo* and Lijun Bian*
Department of Chemistry, College of Science, Northeast University, Shenyang,
Liaoning, 110819, People’s Republic of China
Sulfur vacancies rich CdS based composite photocatalyst with g-C3N4 as matrix has
been synthesized from tetranuclear Cd-S cluster assembled supramolecular network.