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Boron Carbon Nitride Semiconductors Decorated with CdS Nanoparticles for

Photocatalytic Reduction of CO2

Article in ACS Catalysis · April 2018

DOI: 10.1021/acscatal.8b00104

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Cite This: ACS Catal. 2018, 8, 4928−4936 pubs.acs.org/acscatalysis

Boron Carbon Nitride Semiconductors Decorated with CdS

Nanoparticles for Photocatalytic Reduction of CO2
Min Zhou,† Sibo Wang,† Pengju Yang,† Caijin Huang,† and Xinchen Wang*,†,‡
†
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350002,
People’s Republic of China
‡
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
*
S Supporting Information

ABSTRACT: Ternary boron carbon nitride (BCN) semiconductors

have been developed as emerging metal-free photocatalysts for visible-
light reduction of CO2, but the achieved efficiency is still not satisfying.
Herein, we report that the CO2 photoreduction performance of a bulk
BCN semiconductor can be substantially improved by surface engineer-
ing with CdS nanoparticles. The CdS/BCN photocatalysts are
characterized completely by diverse tests (e.g., XRD, FTIR, XPS, DRS,
SEM, TEM, N2 sorption, PL, and transient photocurrent spectroscopy).
Performance of the CdS/BCN heterostructures is evaluated by reductive
CO2 conversion reactions with visible light under benign reaction
conditions. Compared with bare BCN material, the optimized CdS/BCN
photocatalyst exhibits a 10-fold-enhanced CO2 reduction activity and
high stability, delivering a considerable CO production rate of 12.5 μmol
h−1 (250 μmol h−1 g−1) with triethanolamine (TEOA) as the reducing agent. The reinforced photocatalytic CO2 reduction
activity is mainly assigned to the obviously improved visible-light harvesting and the greatly accelerated separation/transport
kinetics of light-triggered electron−hole pairs. Furthermore, a possible visible-light-induced CO2 reduction mechanism is
proposed on the basis of photocatalytic and photo(electro)chemical results.
KEYWORDS: boron carbon nitride, CO2 reduction, CdS, heterostructure, photocatalysis

■ INTRODUCTION
The construction of clean and renewable energy systems is
attracting significant research attention in the 21st century so as
to overcome the great demand of limited fossil fuels for energy
provision.1−7 Reductive conversion of CO2 into added-value
products by sunlight is promising in the exploration of new
alternatives for sustainable energy supply, which is also
accompanied by enormous positive effects to relieve the global
warming effect.8−14 Up to date, a wealth of transition metal
materials, as well as their hybrids, have been employed as
photocatalysts for solar CO2 fixation with encouraging
achievements. However, most of the examined materials (e.g.,
TiO2,7,15−17 ZrO2,18 MgO,19 Ga2O3,20 ZnGa2O4,21 Zn2GeO422)
can only respond to UV light, which seriously limits the
utilization of solar energy. Therefore, it is highly desirable for
developing efficient and stable photocatalysts responsive to
visible light, particularly the candidates made of lightweight and
abundant elements, to operate the reduction of CO2 from the
viewpoint of practical applications.23−25
The metal-free hexagonal boron nitride (h-BN), featuring
high thermal and chemical stabilities, is a wide bandgap
semiconductor.26,27 We have recently demonstrated that the
physicochemical properties of h-BN can be readily tuned
through carbon doping, producing the new semiconductor
material, namely boron carbon nitride (BCN).28 The ternary
BCN semiconductor possesses a conjugated sp2 hybridized
electron system with carbon incorporated into the lattice. By
adjusting the degree of carbon incorporation, the bandgap of
BCN could be delicately modulated to optimize the catalytic
functions. The BCN semiconductor is revealed to be an active
photocatalyst for target photoredox reactions with visible light,
such as H2O splitting and CO2 reduction.28 When cooperating
with a ruthenium photosensitizer, the BCN catalyst manifests a
considerably strong performance for reductive splitting of CO2
into CO under mild conditions. Although BCN displays great
opportunities for photocatalytic CO2 transformation, the
involvement of a ruthenium dye photosensitizer hampers the
sustainable development of the established system. In addition,
the quantum yield of BCN for CO2 photoreduction still needs
to be further upgraded for practical implementation.
The weak optical absorption in the visible-light region and
the high recombination of photoexcited charges are the main
reasons for great restriction of the efficiency of the BCN
semiconductor for CO2 reduction photocatalysis. To fully
activate the potential of the conjugated BCN photocatalyst, our
research effort is concentrated on the development of BCN
Received: January 9, 2018
Revised: April 17, 2018
Published: April 23, 2018

© XXXX American Chemical Society 4928 DOI: 10.1021/acscatal.8b00104

ACS Catal. 2018, 8, 4928−4936
ACS Catalysis
Figure 1. (a) XRD patterns and (b) FT-IR spectra of BCN and CdS/BCN samples.
composite materials with suitable semiconductor light harvest-
ers aiming to enhance photoabsorption and promote charge
transfer kinetics, simultaneously.29−35 As an important visible
light transducer, the CdS semiconductor exhibits high optical
response and has been widely applied as a photoharvester for
diverse photoredox catalysis.36−46 Therefore, we are inspired to
employ CdS nanoparticles to hybridize with a BCN semi-
conductor to assemble CdS/BCN heterostructures for
reductive CO2 conversion.
Herein, CdS/BCN hybrids are prepared through a facile
photodeposition process,39,41 and are completely investigated
by various tests (e.g., XRD, FTIR, XPS, DRS, SEM, TEM, and
N2 adsorption measurements). When evaluated as photo-
catalysts for visible-light CO2 conversion, the optimal CdS/
BCN heterostructure shows considerably strong performance
for deoxygenative reduction of CO2 with a CO formation rate
of 12.5 μmol h−1 (250 μmol h−1 g−1), which is substantially
enhanced by 10-fold when comparing with the bare BCN
material. Moreover, no evident decrease in the catalytic
performance of CdS/BCN is observed after repeated operation
for five cycles. The enhanced performance of reductive CO2
photosplitting is attributed to the obviously boosted photo-
absorption and greatly accelerated transfer kinetics of light-
stimulated electron−hole pairs. Furthermore, a possible visible-
light-induced CO2 reduction mechanism is proposed on the
basis of photocatalytic and photo(electro)chemical results.
■
EXPERIMENTAL SECTION
Materials. Boric acid (H3BO3) was obtained from Aladdin
Biological Technology Co., Ltd. (Shanghai). Cadmium chloride
(CdCl2·2.5H2O), elemental sulfur (S8), urea (H2NCONH2),
cobalt chloride (CoCl2), starch (C12H22O11), bipyridine (bpy),
silicon dioxide (SiO2), ethanol (C2H5OH), triethanolamine
(TEOA), acetonitrile (MeCN), N,N-dimethylformaide (DMF),
dichloromethane (DCM), and tetrahydrofuran (THF) were
purchased from Sinopharm Chemical Reagent Co., Ltd.
(Shanghai, China). High-purity CO2 and nitrogen (N2) gas
(99.999%) were provided by Fuzhou Lianzhong Industrial
Gases Co., Ltd. The 13CO2 was 97% in purity.
Synthesis of BCN. Boron acid, urea, and starch (weight
ratio: 1:2:5) were ground fully with an agate mortar, followed
by a heat treatment in an ammonia atmosphere at 1250 °C for
5 h.28 After calcination, the obtained products were washed
with hot HCl solution (80 °C, 60 mL, 0.1 M) to eliminate the
remaining B2O3, and the obtained sample was denoted as BCN.
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Synthesis of CdS/BCN. BCN (100 mg), S8 (9 mg), and
CdCl2·H2O (60 mg) were dispersed in 80 mL of ethanol under
the protection of a N2 atmosphere. Then, the resultant mixture
was exposed to light illumination (λ > 420 nm) for 30, 60, and
90 min, respectively.39,41 After photodeposition, the obtained
products were rinsed with ethanol and H2O several times to
remove the unreacted raw materials. The obtained samples
were labeled as CdS/BCN-30, CdS/BCN-60, and CdS/BCN-
90, respectively. Unless otherwise stated, the used sample for
characterizations and photocatalysis was the CdS/BCN-60
sample. The reference CdS samples were synthesized through a
similar photodeposition method with inactive SiO2 as the
support, and the obtained sample was designated as CdS-60.
Characterization. Powder X-ray diffraction (XRD) tests
were carried out on a Bruker D8 Advance X-ray diffractometer
(Cu Kα1 radiation, λ = 1.5406 Å). A Nicolet (thermos Nicolet
Nexus) 670 FTIR spectrometer was employed to collect the
Fourier transform infrared (FTIR) spectra. X-ray photoelectron
spectroscopy (XPS) analysis was operated on a PHI Quantum
2000 XPS system with C 1s binding energy (284.6 eV) as the
reference. A Vario MICRO was used to conduct the elemental
analysis of samples. Inductively coupled plasma mass
spectrometry (ICP-MS) measurements were manipulated on
XSRIES 2. Field-emission scanning electron microscopy (SEM,
Hitachi New Generation SU8010) and transmission electron
microscopy (TEM, JEOL model JEM 2010 EX) were utilized
to examine the morphologies of the samples. Optical
absorption of the materials was determined by a Varian Cary
500 Scan UV−vis spectrophotometer, and barium sulfate was
used as the reference. The room temperature photolumines-
cence (PL) characterizations were carried out on an Edinburgh
FI/FSTCSPC 920 spectrophotometer. The average lifetime τ =
(A1τ12 + A2τ22 + A3τ32)/(A1τ1 + A2τ2 + A3τ3).47 N2 sorption
tests were conducted on a Micromeritics ASAP2020. A BAS
Epsilon Electrochemical System was used to perform the
electrochemical analysis in a three-electrode cell (counter
electrode, Pt plate; reference electrode, Ag/AgCl). Fluorine−
tin oxide (FTO) glass was used as the conductive substrate to
prepare the working electrode. Typically, the sample (5 mg)
was totally dispersed in DMF (1 mL) by sonication to gain a
slurry. Afterward, the resultant slurry was spread onto the FTO
glass with an area of ca. 0.25 cm2. The transient photocurrent
response spectra were collected in Na2SO4 aqueous solution
(0.2 M) with a 300 W xenon lamp (λ ≥ 420 nm) as a light
source, and the applied bias potential was −0.4 V vs Ag/AgCl
(pH = 6.8).
DOI: 10.1021/acscatal.8b00104
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ACS Catalysis
Figure 2. XPS spectra of CdS/BCN-60 (a) survey spectrum and the high resolution spectrum of (b) B 1s, (c) C 1s, (d) N 1s, (e) Cd 3d, and (f) S
2p.
Measurements. Products of CO2 photoreduction reactions
were analyzed by an Agilent 7820A gas chromatograph (GC;
thermal conductivity detector, TCD; TD-01 packed column;
oven temperature, 50 °C; inlet temperature, 120 °C; detector
temperature, 200 °C). Ar was used as the carrier gas (13 mL
min−1). The CO gas produced from 13CO2 isotope experiments
was examined by a gas chromatograph−mass spectrometer
(GC-MS, HP 5973). The equipped column in GC-MS analysis
was HP-MOLESIEVE (Agilent Technologies, 30 m × 0.32 mm,
serial number: USD 130113H). The temperatures of the inlet
and oven were 200 and 45 °C, respectively. Helium (He) was
used as a carrier gas (0.6 mL min−1).
Photocatalytic Test. In a typical photocatalytic CO2
reduction reaction, photocatalyst (50 mg), bpy (20 mg),
solvent (6 mL, acetonitrile/H2O = 2:1), TEOA (1 mL), and
CoCl2 (1 μmol) were added into a gas-closed quartz glass
reactor (80 mL in volume). The reaction system was filled with
high purity CO2 gas (1 atm). A 300 W Xe lamp was used as the
light source with the incident light controlled by a 420 nm
long-pass cutoff filter, and the irradiation window of the reactor
was ca. 6 cm2. Cooling water was employed to keep the
reaction temperature at 40 °C. During photocatalysis, the
reaction system was energetically stirred. After reaction, the
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generated gaseous products (CO and H2) were sampled and
quantified by the GC. The cycle experiments were conducted
by directly recovering the used catalysts and then redispersing
the catalysts into a fresh solution.
■ RESULTS AND DISCUSSION
Power XRD characterizations are first conducted to analyze the
crystal structure and phase of as-prepared CdS/BCN
composites. The peak position in XRD pattern (Figure 1a) of
pristine BCN is consistent with the results of reported
works.28,44,48 The characteristic XRD peak located at 2θ of
26° is ascribed to the (002) plane of BCN, while the other peak
at 43° is attributed to the (100) plane of BCN. After
modification with CdS, the peak position of BCN is unchanged,
but the peak intensity is decreased slightly, indicating the basic
graphitic structure of BCN is maintained well in the final CdS/
BCN materials. The characteristic diffraction peaks of CdS are
clearly observed in the XRD pattern of CdS/BCN-90, which
are perfectly indexed to the crystal planes of hexagonal CdS.39
These observations suggest that the crystal structures of CdS
and BCN are well developed in the CdS/BCN samples. The
chemical structures of CdS/BCN are examined by FTIR
spectroscopy. As shown in Figure 1b, the characteristic
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ACS Catalysis Research Article

variations assigned to typical BCN material are clearly seen for

all the samples, revealing the successful evolution of BCN
structure. The vibration of in-plane B−N bonds is located at
1380 cm−1, and the other location at 780 cm−1 is assigned to
the out-of-plane B−N−B bending vibration.49,50
To justify the molar ratio of the BCN material, elemental
analysis is performed. The results (Table S1) show that the
molar ratio of B/C/N in the boron carbon nitride sample is ca.
8.5:1.0:5.9, that is, the empirical formula of the boron carbon
nitride semiconductor is B8.5CN5.9, designated as BCN for
clarity. The surface chemical compositions and valence states of
elements in CdS/BCN-60 are studied by XPS.50−52 The
presence of B, C, N, Cd, and S elements is discerned in the
survey spectrum (Figure 2a). The B 1s high-resolution XPS
spectrum is resolved into three subpeaks with binding energies
of 189.8, 190.4, and 192.0 eV, ascribed to B−C, B−N, and B−
O bands, respectively (Figure 2b). In the result of XPS analysis
for C 1s (Figure 2c), the peaks located at 283.5, 284.6, and
286.2 eV belong to C−B, C−C, and C−N bonds. Figure 2d
shows the N 1s XPS spectrum, in which the three peaks
centered at 397.9, 398.6, and 400.5 eV are ascribed to the
binding energy of N−B, N−C, and N−H bonds. As for the Cd
3d high resolution XPS spectrum (Figure 2e), the spin orbit of
Cd 3d5/2 locates at around 405.41 eV, while the Cd 3d3/2 peak Figure 3. SEM images of (a) BCN and (b) CdS/BCN-60. (c) TEM
and (d) HRTEM images of CdS/BCN-60.
lies at 412.20 eV. The spin orbit separation (Δ) of the Cd 3d
orbital is 6.79 eV, which demonstrates that the valence state of
(Figure S4), pointing to the porous features of the materials.
the Cd element in CdS/BCN is Cd2+.39,41 In addition, the
However, compared with unmodified BCN, the BET surface of
signal peaks positioned at 161.5 and 162.9 eV in the S 2p
CdS/BCN-60 is decreased. This is because CdS nanoparticles
spectrum (Figure 2f) are S 2p1/2 and S 2p3/2 spin orbits,
alter the basic texture and surface morphology of BCN support
indicating that the S2− state exists in the sample.39,53−55 The
(e.g., collapse/block of mesopores), resulting in the reduction
peak locations of Cd2+ and S2− in the XPS spectra are in
in surface area.
accordance with CdS in a reported work.39 The amounts of Optical absorption of BCN and CdS/BCN materials are
CdS in the final materials are determined by elemental analysis checked by DRS. All the samples show the classic semi-
and ICP measurements. Results indicate that the amounts of conductor light absorption features (Figure 4). In the optical
CdS in the CdS/BCN-30, CdS/BCN-60, and CdS/BCN-90
samples are 8.09, 13.25, and 16.62 wt %, respectively (Table
S2).
SEM, TEM, and N2 sorption tests are carried out to obtain
more details about morphological and porous characteristics of
CdS/BCN hybrids. Figure 3a demonstrates the SEM images of
bare BCN. The size distributions of BCN and CdS particles are
presented in Figures S1 and S2. In the SEM image of CdS/
BCN (Figure 3b), some small nanoparticles are clearly seen
compared to that of the bare BCN (Figure 3a and Figure S2a),
indicating CdS nanoparticles are tightly coupled on the BCN
surface. The CdS/BCN sample is further examined by TEM
(Figure 3c). Figure 3d indicates the high-resolution TEM
(HRTEM) image of CdS/BCN, and the distinct lattice fringes
reflect the well-defined crystal structures of CdS and BCN in
the composite. The lattice fringe with d spacing of 0.352 nm is
identified for the (002) crystal plane of hexagonal CdS,39 while
the lattice spacing of 0.34 nm is indexed to the (002) interlayer
of BCN.28 To study the dispersion and distribution of the Figure 4. DRS spectra of BCN and CdS/BCN samples.
components, elemental mapping characterizations are per-
formed. As shown in Figure S3, B, C, N, Cd, and S elements are range lower 500 nm, the CdS/BCN samples exhibit a major
witnessed, reflecting that the CdS nanoparticles are evenly light absorption in comparison with BCN. However,
deposited and distributed on the surface of a BCN semi- composting of CdS nanoparticles may not change the inherent
conductor. SEM and TEM characterizations further confirm the band structure of BCN semiconductor, because the decoration
successful fabrication of CdS/BCN hybrid materials. N2 of small quantity of CdS nanoparticles does not alter the
sorption tests are conducted to gain information about surface structure of BCN semiconductor. The enhanced optical
properties and porous characteristics of the CdS/BCN sample. response of visible light is mainly benefited from the
Both BCN and CdS/BCN-60 samples exhibit the type IV sensitization effect of CdS nanoparticles. The increased visible
sorption isotherms of N2 with an H1 type hysteresis loop light absorption greatly contributes to the harvesting of
4931 DOI: 10.1021/acscatal.8b00104
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ACS Catalysis
Figure 5. (a) Room-temperature PL spectra, (b) transient photocurrent response, (c) time-resolved PL spectra, (d) EIS Nyquist plots of BCN and
CdS/BCN-60 samples.
Figure 6. (a) Photocatalytic CO2 reduction performance of different samples and (b) time-yield plots of CO and H2 over CdS/BCN-60 sample.
photons, and typically favorable for boosting photoredox
catalysis such as CO2 photoreduction. The band gap of BCN
is about 2.64 eV determined from the Tauc plot (Figure S5b).
The conduction band (CB) position of BCN is around −0.56 V
calculated from the Mott−Schottky plot (Figure S5c).28,56,57
Thus, the valence band (VB) of BCN is 2.08 V. It has been
proved the CB and VB positions of CdS are ca. −1.01 and 1.39
V, respectively.58 Therefore, the band structures of BCN and
CdS are determined (Figure S5d).
The separation−recombination rate of the light-generated
charges on BCN and CdS/BCN-60 is investigated by PL and
transient photocurrent response analysis. In the PL spectra
(Figure 5a), the center of the broad emission peak for bare
BCN is ca. 520 nm. Strikingly, the PL intensity of CdS/BCN-
60 is substantially diminished. The finding suggests that the
recombination rate of photoinduced electron−hole pairs is
greatly reduced, mainly due to the construction of an adaptive
4932
Research Article
heterojunction between BCN and CdS to realize a built-in
electric field to promote charge transfer. In addition, the
decrease in PL intensity may also be compatible with the fast
quenching of an excited state in principle.56,59 The charge
separation of CdS/BCN is further demonstrated by photo-
(electro)chemical experiments.60,61 In the results of transient
photocurrent spectra (Figure 5b), the current intensity of CdS/
BCN-60 is evidently higher than that of bare BCN, which
strongly indicates the enhanced mobility of charge carriers over
the composite materials.62,63 PL lifetimes analysis demonstrates
that the average lifetime of CdS/BCN-60 is 5.08 ns and the
lifetime of pure BCN is 4.49 ns at 298 K (Figure 5c). The
average PL lifetime can be regarded as a crude yet rational
indicator to estimate the separation efficiency of photoexcited
charge carriers. This result reveals that CdS decorated BCN
samples can offer more free charges to catalyze surface redox
reactions. Additionally, an electrochemical impedance spectros-
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ACS Catalysis
Figure 7. Results of GC-MS analysis of the CO generated from the 13CO2 isotope experiments: (a) GC spectrum and (b) MS spectrum.
Figure 8. (a) Production of CO/H2 in the stability tests of CdS/BCN-60 sample and (b) powder XRD patterns of fresh and used CdS/BCN-60
samples.
copy (EIS) study demonstrates that CdS/BCN-60 manifests a
reduced semidiameter in the Nyquist plots (Figure 5d),
suggesting the fast interfacial charge transfer of the hetero-
structured material. These results of photo(electro)chemical
measurements validate that prolonged lifetime and accelerated
separation/transport kinetics of photogenerated charges are
realized for the CdS/BCN-60 sample, which are highly
desirable for reductive CO2 transformation reactions.
The above-mentioned results demonstrate that CdS
decoration is effective in adjusting the texture, optical and
electronic properties of the metal-free BCN semiconductor and
thus should improve the performance of BCN for target
photoredox catalysis. The catalytic performance of the CdS/
BCN composites is evaluated by visible-light-driven reductive
CO2 conversion reactions carried out in a H2O/MeCN mixture
with TEOA as the electron donor and Co(bpy)32+ as the
cocatalyst. As shown in Figure 6a, the pristine BCN only
exhibits moderate activity (1.2 μmol h−1, 24 μmol h−1 g−1) for
the CO2-to-CO transformation reaction in the established
catalytic system. Once CdS nanoparticles are decorated on
BCN, the CdS/BCN-30 sample exhibits considerably improved
activity. Further increasing the deposition amount of CdS
nanoparticles, the CdS/BCN-60 sample affords the highest
CO2 reduction activity, manifesting a CO-yielding rate of 12.5
μmol h−1 (250 μmol h−1 g−1), which is more than 10 times
higher relative to the pristine BCN material. If excessive CdS
nanoparticles are deposited on BCN, the catalytic performance
of the CdS/BCN-90 sample is however decreased, which may
be caused by the light-shielding effect of CdS nano-
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particles.41,42,64,65 The time-production plots of CO and H2
demonstrate that the reaction rate is almost unchanged during
the first hour of reaction (Figure 6b). The control experiments
indicate no CO2 reduction catalysis is observed when the
reaction system is manipulated without the presence of visible
light or TEOA (Table S3). Without CO2, only a small amount
of H2 is produced from the reaction system, which suggests that
the formed CO is derived from CO2 photoreduction. (Table
S3, entry 6). In addition, without cobalt/bpy (Table S3, entry
3) or the CdS/BCN-60 catalyst (Table S3, entry 1), no CO and
H2 are detected. Methanol and ethanol are also applied as
alternative electron donors for the CO2 reduction reaction, but
no detectable CO/H2 is produced (Table S3, entries 7−8).
Furthermore, the photocatalytic CO2 reduction performance of
CdS-60 is evaluated, and the results indicate that only 3.9 μmol
of CO and 0.7 μmol of H2 are produced from the reaction
system under identical conditions, affording a CO selectivity of
84.8% (Table S3, entry 2). Obviously, the CO2 reduction
reactivity of the CdS-60 sample is much more inferior to that of
CdS/BCN samples (Table S3, entries 9−11), but the selectivity
of CO is comparable. The low activity of CdS-60 should be
related to inefficient electron−hole separation/transfer and
limited active sites.65,66 Reaction temperature and solvents of
the catalytic system are also optimized to realize efficient
photocatalytic CO2 reduction. Results reveal that the CO2
reduction system obtains the highest activity with H2O/MeCN
as the reaction solvent under a reaction temperature of 40 °C
(Figures S6 and S7).
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The carbon origin of the CO product generated from the
CO2 photosplitting system is confirmed with a 13C-labeled
isotopic experiment. The results of GC-MS tests for the 13CO
are presented in Figure 7. As shown, the peak at 3.27 min in the
GC spectrum (Figure 7a) with a m/z value of 29 in the MS
spectrum (Figure 7b) is assigned to 13CO. The findings
evidence that the generated CO is completely stemmed from
reductive CO2 deoxygenation, and therefore, excluding the
possibility from other carbon-containing substances in the
system. To examine the potential generation of liquid phase
products, the supernatant of the reaction system is cross-
checked by diverse analysis (e.g., ion chromatography, GC-MS
and 13C NMR spectroscopy). It is confirmed that no detectable
liquid products such as formic acid and methanol are generated.
Such a product distribution is in line with results of reported
works.6,9,13,14,42,67
To check the stability of the hybrid photocatalyst, the CdS/
BCN-60 solid is filtrated after photocatalysis and then
recovered and added into fresh reaction mixtures for cycling
CO2 reduction operations. No substantial reduction of CO/H2
is noticed during five cycles (Figure 8a). In the fifth CO2
reduction reaction, the CO evolution of CdS/BCN-60 can still
retain 80% of the initial activity. The decrease in CO2
photoreduction activity is mainly because of the inevitable
loss of the photocatalyst during the multistep recovery
processes. However, the control experiment demonstrates
that stability of the CdS/BCN-60 composite for CO2
photoconversion is much superior to that of the bare BCN
sample (Figure S8). Moreover, after photocatalysis, the used
CdS/BCN-60 sample is further analyzed by XRD (Figure 8b)
and FTIR (Figure S9). The observations reveal that the CdS/
BCN-60 hybrid experiences no noticeable alternation in crystal
and chemical structures, reaffirming the high stability of the
CdS/BCN heterojunction photocatalyst for the reaction.
As last, a probable mechanism of the reductive CO2 splitting
reaction catalyzed by the CdS/BCN heterostructure is
proposed (Scheme 1). The electron−hole pairs are generated
on BCN and CdS semiconductors under illumination with
visible light. Because CdS possesses a CB more negative than
that of BCN, it results in the formation of an internal electric
field within the space charge region, which can effectively assist
the separation and migration of photoinduced electron−hole
charges. Consequently, the excited electrons (e−) can migrate
Scheme 1. Possible Reaction Mechanism for CO2
Photoreduction by CdS/BCN Heterostructure
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Research Article
rapidly from the CB of CdS to that of BCN. The accumulated
electrons will react with the adsorbed CO2 molecules on CdS/
BCN surface to produce CO. Meanwhile, the H+ in the
chemical system can be reduced by electrons as well, leading to
the formation of H2. The holes (h+) are facilitated to transform
from the VB of BCN to that of CdS and ultimately quenched
by reducing agent TEOA. Therefore, the redox cycle of the
reductive CO 2 photoconversion reaction is accom-
plished.28,29,41,42,53
■ CONCLUSION
In summary, we report the facile fabrication of CdS/BCN
heterostructured photocatalysts for efficient reductive CO2
deoxygenation to CO with visible light under moderate
conditions. The as-prepared CdS/BCN hybrids are completely
characterized by various physicochemical tests. The optimized
CdS/BCN composite photocatalyst exhibits 10-fold-enhanced
CO2-to-CO conversion activity together with high stability,
compared to the pristine BCN material. The reinforced
photocatalytic CO2 reduction efficiency is primarily assigned
to the obviously improved visible-light harvesting and the
greatly accelerated separation and transfers of photoinduced
charge carriers. This work demonstrates that the CO2
photoreduction performance of the emerging BCN photo-
catalyst can be substantially enhanced by surface modification
with traditional semiconductors (e.g., CdS) to form hetero-
structures. It is anticipated that this work should bring
prodigious opportunities to artificial photosynthesis by rational
design and engineering of the conjugated BCN semiconductors
to modulate their optical, physical, and chemical properties to
enhance the performance of target photoredox reactions (e.g.,
H2O splitting, CO2 fixation, and organic synthesis).
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.8b00104.
Additional photocatalyst characterization data (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: xcwang@fzu.edu.cn.
ORCID
Sibo Wang: 0000-0003-2656-9169
Xinchen Wang: 0000-0002-2490-3568
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work is financially supported by the National Natural
Science Foundation of China (Grant Nos. 21425309,
21761132002, U1662112), the National Postdoctoral Program
for Innovative Talents (BX201600031), the China Postdoctoral
Science Foundation (2017M612116), and the 111 Project.
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4936 DOI: 10.1021/acscatal.8b00104

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