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Published: October 20, 2011

r2011 American Chemical Society 23501 dx.doi.org/10.1021/jp208661n


|
J. Phys. Chem. C 2011, 115, 2350123511
ARTICLE
pubs.acs.org/JPCC
Assembly of CdS Nanoparticles on the Two-Dimensional Graphene
Scaffold as Visible-Light-Driven Photocatalyst for Selective Organic
Transformation under Ambient Conditions
Nan Zhang, Yanhui Zhang, Xiaoyang Pan, Xianzhi Fu, Siqi Liu, and Yi-Jun Xu*
State Key Laboratory Breeding Base of Photocatalysis, and College of Chemistry and Chemical Engineering, Fuzhou University,
Fuzhou 350002, P. R. China
1. INTRODUCTION
Selective oxidation of alcohols to carbonyls is a fundamental but
signicant transformation of great industrial importance, because
carbonyl compounds such as aldehyde and ketone derivatives are
widely utilized in the fragrance, confectionary, and pharmaceutical
industries.
19
Conventional organic synthesis for the partial oxida-
tion of alcohols into corresponding aldehydes or ketones not only
involves environmentally and corporally harmful, toxic, or corrosive
stoichiometric oxidants and harsh conditions, such as chromate,
permanganate, high temperature and pressure, but also pro-
duces quantities of hazardous wastes.
912
In order to conquer
these shortcomings, enormous attention has been devoted to
exploiting clean processes for organic synthesis.
515
Photocatalysis,
which is originated from the breakthrough made by Fujishima and
Honda in 1972,
16
as a green technique provides an alternative to the
conventional synthetic pathways.
7
The required mild conditions and
the possibility to decrease the generation of undesired substances
highlight its potential as a promising route for organic synthesis.
Thus, increasing eorts are being paid to photocatalytic selective
oxidation of alcohols.
19,15,1720
For instance, Zhang et al. have
designed an ingenious coupled system consisting of dye-sensitized
TiO
2
and 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) for visible-
light-induced aerobic oxidation of alcohols to corresponding
aldehydes with high selectivity.
1
It has been reported that home-
prepared TiO
2
catalyst shows photoactivity for selective oxidation of
aromatic alcohols under the UV light irradiation.
15,1921
However, a
literature survey leads us to the nding that most of the reports on
photocatalysis used for selective oxidation of alcohols are focused
on TiO
2
or TiO
2
-based materials.
15,15,1829
In the long run, one
of the challenges as well as opportunities faced by the researchers is
to develop other novel visible-light-driven photocatalysts used for
selective organic transformations.
In recent decades, as a well-known IIVI semiconductor, CdS
has been extensively studied due to its suitable band gap (2.4 eV)
corresponding well with the spectrumof sunlight,
30
size-dependent
electronic and optical properties,
31
and diverse applications, such
as biological sensors,
3234
solar cells,
3537
eld-eect transistors
(FET),
38,39
environment purication,
40,41
and hydrogen
evolution.
4249
Nevertheless, there are still several issues that
limit the utilization of pure CdS particles. For example, CdS
particles are prone to aggregation, resulting in a reduced surface
area.
48
High recombination rate of photogenerated electronhole
Received: September 8, 2011
Revised: October 20, 2011
ABSTRACT: A series of cadmium suldegraphene (CdSGR) nanocomposites
with dierent weight addition ratios of graphene (GR) have been synthesized via a
facile one-step hydrothermal approach, during which the formation of CdS nano-
particles and the reduction of graphene oxide (GO) occur simultaneously. X-ray
diraction (XRD), UVvis diuse reectance spectra (DRS), eld-emission scan-
ning electron microscopy (FE-SEM), transmission scanning electron microscopy
(TEM), energy-dispersive X-ray spectroscopy (EDX), nitrogen adsorptiondesorp-
tion, photoluminescence spectra (PL), andelectronspinresonance spectra (ESR) are
employed to determine the properties of the samples. It is found that the CdS
nanoparticles evenly overspread on the graphene scaold, and the properties of the
samples, including morphology, pore structure, optical, and electronic nature, are able
to be tuned by the addition of GR as compared with blank-CdS prepared in the
absence of GR. The photocatalytic activities of the as-prepared CdSGR nanocom-
posites are evaluated by selective oxidation of a range of alcohols under mild conditions. To our best knowledge, it is the rst time to use
CdSGR nanocomposites as visible light photocatalyst for selective organic transformation. Our results demonstrate that the as-prepared
CdSGR nanocomposites can serve as a promising visible-light-driven photocatalyst for selective oxidation of alcohols to corresponding
aldehydes. The high photoactivity of CdSGRcan be ascribed to the integrative eect of enhanced light absorption intensity, high electron
conductivity of GR, and its signicant inuence on the morphology and structure of the samples. It is hoped that our current work could
widen the application of CdSGR nanocomposites and open promising prospects for the utilization of GR-based semiconductor
nanocomposites as visible light photocatalyst for selective organic transformations.
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The Journal of Physical Chemistry C
ARTICLE
pairs is another problem to restrict its wide application.
50
There-
fore, improvement of the performance of CdS has been the
subject of numerous studies. Many attempts have been explored
to enhance the activity of CdS particles, such as synthesis of CdS
quantum dots
51,52
and combination with other components,
including noble metals,
5357
semiconductors,
5863
and carbon
materials.
49,50,6469
Among the promising carbon materials, graphene (GR), a
at monolayer of carbon atoms tightly packed into a two-
dimensional (2D) honeycomb crystal structure, is expected to
have great potential as a nanoscale building block for develop-
ing hybrid materials due to its unique sheet morphology,
ultrahigh electron conductivity, and mobility.
70,71
Over the
past few years, the burgeoning interests in graphene-based
hybrid materials have been spurred by the continuous progress
of nanotechnology in materials science.
7276
Among the abun-
dant graphene-based nanocomposites, grapheneCdS has
widely received attention for its combination of two promising
components.
48,49,6466,7783
For instance, Cao et al.
65
have
reported a facile route to prepare grapheneCdS quantum dot
nanocomposites using dimethyl sulfoxide (DMSO) as solvent
and the source of sulfur. In their work, a picoseconds ultrafast
electron transfer process from the excited CdS to the graphene
sheet has been detected. Afterward, Li et al.
48
utilized a similar
method to synthesize CdS-cluster-decorated graphene nano-
sheets for photocatalytic hydrogen production under visible light
irradiation. A layered graphene/quantum dot (QD) based elec-
tron transfer system has been created by a bottom-up approach,
in which CdS QDs were chosen as the model.
77
Although there
have been some reports on grapheneCdS nanocomposites, it
should be noted that they always focus on the study of optical,
electronic properties or application in photocatalytic hydrogen
evolution.
48,49,6366,7782
The utilization of grapheneCdS
nanocomposites in selective organic synthesis is still open and
remains to be evaluated.
Herein, we fabricate grapheneCdS (GRCdS) nanocom-
posites with dierent weight addition ratios of GR via a facile
DMSO method
48,65
and utilize them for photocatalytic selec-
tive oxidation of a range of alcohols under ambient conditions.
To our best knowledge, it is the rst time to apply GRCdS
nanocomposites to photocatalytic selective oxidation. The
results demonstrate that the as-prepared GRCdS nanocom-
posite can serve as a promising photocatalyst for selective
oxidation of various alcohols to corresponding aldehydes.
The present research work is intended to provide the reader-
ship with ternary information. First, besides its applications in
optoelectronic eld and hydrogen evolution, GRCdS nano-
composite is able to be used as visible light photocatalyst in
selective oxidation of alcohols under ambient conditions. The
high photoactivity of CdSGR can be ascribed to the integra-
tive eect of enhanced light absorption intensity, high electron
conductivity of GR, and its signicant inuence on the mor-
phology and structure of the samples. Second, the content of
GR has a great eect on the morphology and photoactivity of
the as-prepared GRCdS nanocomposites; a high weight
addition ratio of GR in the nanocomposites could lead to a
deterioration of the photocatalytic performance, and the opti-
mal ratio of GRmay dier in specic reaction systems. Finally, it
is expected that our work could open the doorway for the
exploration on GRCdS and other GR-based semiconductor
nanocomposites for visible-light-driven photocatalytic selective
organic transformations.
2. EXPERIMENTAL SECTION
2.1. Preparation. Materials. Cadmiumacetate (Cd(CH
3
COO)
2
3
2H
2
O), dimethyl sulfoxide (C
2
H
6
OS
2
), graphite powder, sulfuric acid
(H
2
SO
4
), nitric acid (HNO
3
), hydrochloric acid (HCl), potassium
persulfate (K
2
S
2
O
8
), phosphorus pentoxide (P
2
O
5
), potassium per-
manganate (KMnO
4
), hydrogen peroxide, 30%(H
2
O
2
), and ethanol
(C
2
H
6
O) were obtainedfromSinopharmChemical Reagent Co., Ltd.
(Shanghai, China). All materials were used as received without further
purification.
Synthesis. (a) Synthesis of Graphene Oxide (GO). Graphene
oxide (GO) was synthesized from natural graphite powder by a
modified Hummers method.
73,84
In detail, 2 g of graphite powder
was put into a mixture of 12 mL of concentrated H
2
SO
4
, 2.5 g of
K
2
S
2
O
8
, and 2.5 g of P
2
O
5
. The solution was heated to 80 C in
an oil bath kept stirring for 24 h. The mixture was then carefully
diluted with 500 mL of deionized (DI) water, filtered, and
washed until the pH of rinse water became neutral. The product
was dried under ambient condition overnight. This preoxidized
graphite was then subjected to oxidation described as follows. In
a typical procedure, preoxidized graphite powder was added to a
mixture of 120 mL of concentrated H
2
SO
4
and 30 mL of HNO
3
under vigorous stirring, and the solution was cold to 0 C. Then,
15 g of KMnO
4
was added gradually under stirring, and the
temperature of the mixture was kept to be below 20 C by
cooling. Successively, the mixture was stirred at room tempera-
ture for 96 h and then diluted with 1 L of DI water in an ice bath
to keep the temperature below 50 C for 2 h. Shortly after the
further dilution with 1 L of DI water, 20 mL of 30% H
2
O
2
was
then added to the mixture, and a brilliant yellow product was
formed along with bubbling. The mixture was filtered and
washed with 1:10 HCl aqueous solution to remove metal ions
followed by DI water to remove the acid. The filter cake was then
dispersed in water by a mechanical agitation. Low-speed cen-
trifugation was done at 1000 rpm for 2 min. The supernatant
then underwent two more high-speed centrifugation steps at
8000 rpm for 15 min to remove small GO pieces and water-
soluble byproduct. The final sediment was redispersed in water
with mechanical agitation or mild sonication using a table-top
ultrasonic cleaner, giving a solution of exfoliated GO. The GO
separated and dried is in the form of a brown powder. (b)
Fabrication of GRCdS Nanocomposites. The synthesis proce-
dures are based on a modified method as originally reported
by Cao et al. during which the weight addition ratios of GR
was not considered.
65
The process preparation is illustrated in
Scheme 1. The as-prepared GO with the desired weight addition
was dispersed in 40 mL of DMSO by ultrasonication to obtain
the homogeneous GODMSO dispersion. Then, 0.106 g of
Cd(CH
3
COO)
2
3
2H
2
O was added into the above solution. The
mixture was stirred vigorously and then transferred to a 50 mL
Teflon-lined stainless steel autoclave. The solvothermal treatment
Scheme 1. Illustration for Preparation of CdSGR Nano-
composites via a Solvothermal Process
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was conducted at 453 K for 12 h. After that, the products were
cooled at room temperature and separated by centrifugation and
washed with absolute ethanol. Followed by a dry process, a series
of GRCdS nanocomposites with different weight addition ratios
of GR to CdS were obtained. (c) Synthesis of Blank-CdS. Blank-
CdS was synthesized via the same procedure as that of GRCdS
nanocomposites except for the addition of GO.
2.2. Characterization. The crystal phase properties of the
samples were analyzed with a Bruker D8 Advance X-ray diffract-
ometer (XRD) using Ni-filtered Cu K radiation at 40 kV and
40 mA in the 2 ranging from 10 to 80 with a scan rate of 0.02
per second. The optical properties of the samples were characterized
by a Cary 500 UVvisible ultraviolet/visible diffuse reflectance
spectrophotometer (DRS), during which BaSO
4
was employed as
the internal reflectance standard. Field emission scanning electron
microscopy (FE-SEM) was used to determine the morphology of
the samples on a FEI Nova NANOSEM 230 spectrophotometer.
Transmission electron microscopy (TEM) images, high-resolution
transmission electron microscopy (HRTEM) images, and energy
dispersive X-ray spectrum (EDX) were obtained using a JEOL
model JEM2010 EXinstrument at an accelerating voltage of 200 kV.
Nitrogen adsorptiondesorption isotherms and the Brunauer
EmmettTeller (BET) surface areas were collected at 77 K on a
Quantachrome Autosorb-1-C-TCD system. The photolumines-
cence spectra (PL) for solid samples were investigated on an
Edinburgh FL/FS900 spectrophotometer. The electron spin reso-
nance (ESR) signal of the radicals spin-trapped by 5,5-dimethyl-l-
pyrroline-N-oxide (DMPO) was recorded on a Bruker EPR A300
spectrometer. Indetail, the sample (5 mg) was dispersedin0.5 mLof
purified benzotrifluoride into which 25 Lof DMPO/benzyl alcohol
solution (1:10, v/v) was added. The mixture was oscillated to obtain
well-blending suspension. The irradiationsource ( >420 nm) was a
300 W Xe arc lamp system, the very light source for our photo-
catalytic selective oxidation of alcohols. The settings for the ESR
spectrometer were as follows: center field = 3512 G, microwave
frequency = 9.86 GHz, and power = 6.36 mW.
2.3. Activity. The photocatalytic selective oxidation of vari-
ous alcohols was performed as follows. A mixture of alcohol
(0.1 mmol) and 8 mg of catalyst was dissolved in the solvent of
benzotrifluoride (BTF) (1.5 mL), which was saturated with pure
molecular oxygen. The choice of solvent BTF is because of its
inertness to oxidation and high solubility for molecular
oxygen.
1,2,17
The above mixture was transferred into a 10 mL
Pyrex glass bottle filled with molecular oxygen at a pressure of
Figure 1. XRDpatterns (A) and the (220) peak Lorentzian function tting (B) of the as-prepared samples of blank-CdS and CdSGRnanocomposites
with dierent weight addition ratios.
Figure 2. SEM images of the as-prepared samples of (A) blank-CdS,
(B) CdS5% GR, and (C) CdS30% GR nanocomposites.
23504 dx.doi.org/10.1021/jp208661n |J. Phys. Chem. C 2011, 115, 2350123511
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ARTICLE
0.1 MPa and stirred for half an hour to make the catalyst blend
evenly in the solution. The suspensions were irradiated by a 300
WXe arc lamp (PLS-SXE 300, Beijing Trusttech Co. Ltd.) with a
UV-CUT filter to cut off light of wavelength <420 nm. After the
reaction, the mixture was centrifuged at 12 000 rmp for 20 min to
completely remove the catalyst particles. The remaining solution
was analyzed with an Aglient Gas Chromatograph (GC-7820).
The assignment of products was confirmed by a Hewlett
Packard Gas Chromatograph/Mass Spectrometer (HP-5973GC/
MS). Conversion of alcohol, yield of aldehyde, and selectivity for
aldehyde were defined as the follows:
conversion % C
0
C
alcohol
=C
0
100
yield % C
aldehyde
=C
0
100
selectivity % C
aldehyde
=C
0
C
alcohol
100
where C
0
is the initial concentration of alcohol and C
alcohol
and
C
aldehyde
are the concentration of the substrate alcohol and the
corresponding aldehyde, respectively, at a certain time after the
photocatalytic reaction.
3. RESULTS AND DISCUSSION
Figure 1A shows the XRD patterns of the blank-CdS and
CdSGR nanocomposites with dierent weight addition ratios
of GR. It can be seen that the as-prepared blank-CdS and
CdSGR nanocomposites possess similar XRD patterns. All of
these samples give rise to diraction peaks of hawleyite CdS
phase with lattice constant a = 5.818 (JCPDS No. 10-0454).
The peaks at 2 values of 26.506, 43.960, 52.132, and 70.357
can be attributed to the (111), (220), (311), and (331) crystal
planes of hawleyite CdS, respectively. The broad peaks indicate
that the crystallite sizes of CdS nanoparticles in the nanocompo-
sites are small, which can be ascribed to the slow release of
S
2
ions from DMSO, thus forming diminutive CdS crystallite
size.
48
For each sample, the peak width of half-height (fwhm)
for the hawleyite CdS (220) facet is obtained by tting to a
Lorentzian function (Figure 1B). The average crystallite sizes of
CdS particles calculated from the (220) peak of the XRD pattern
by the Scherrer formula are about 2.0, 2.4, 2.7, 2.7, and 2.9 nm,
corresponding to blank-CdS, CdS1% GR, CdS5% GR,
CdS10% GR, and CdS30% GR, respectively. Notably, with
the increase of GR content, the intensity of diraction peaks for
these samples is intensied and the average crystallite size of CdS
nanoparticles is increased. It may be due to the fact that the
introduction of GR can improve crystallinity of CdS nanoparti-
cles because it provides an ideal platform to CdS for its nuclea-
tion. The same phenomenon has been observed in the previous
report.
48
However, there is no apparent peak for the separate GR
in the CdSGR nanocomposites to be detected. This can be
ascribed to two probable causes. One is that the relatively low
diraction intensity of GR at 26.0 might be shielded by the main
peak of hawleyite CdS at 26.5.
48
The other is probably due to
the disappearance of the layer-stacking regularity after redox of
graphite.
49
Scanning electron microscopy (SEM) images are taken to
directly analyze the morphology of the samples and the eect of
Figure 3. Results of TEM (A), HRTEM (B), and EDX (C) for the CdS5% GR nanocomposite; the inset of (B) is the image of the SAED pattern.
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ARTICLE
GR on the samples microscopic structure, as displayed in
Figure 2. It can be observed from Figure 2A that, for the sample
of blank-CdS, spherical CdS particles are obtained with the
average diameter around 200 nm in the absence of GR. When
GO is added during the synthesis of CdSGR nanocomposites,
the morphology of as-formed CdS particles can be chemically
tuned, which is quite dierent from blank-CdS. For example, for
CdS5% GR, the much smaller CdS nanoparticles are obtained,
which spread uniformly on the surface of GR nanosheets
(Figure 2B). Furthermore, it can be seen that the characteristic
layered structure of GR is still retained. However, when the
weight content of GR is increased to 30%, large areas of the GR
sheets without CdS decoration are present which resemble
crumpled silk veil waves, as shown in Figure 2C. The SEM
results indicate that GR nanosheets have a great inuence on the
morphology of the as-prepared CdSGR samples, as reported in
the literature.
48,65
On one hand, GR nanosheets are able to serve
as a two-dimensional mat with which the CdS nanoparticles
interact to hinder the aggregation. On the other hand, comparing
the morphology of CdSGR samples with dierent weight
contents of GR clearly suggest that the introduction of an
appropriate amount of GR to synthesize the CdSGR nanocom-
posite is of great importance for achieving a good and homo-
geneous distribution of CdS nanoparticles on the two-dimensional
GR scaold.
To further obtain the microscopic structure information, trans-
mission electron microscopy (TEM) analysis and energy-dispersive
X-ray spectroscopy (EDX) of the CdS5% GR nanocomposite
have been carried out, as displayed in Figure 3. It can be seen
from Figure 3A that GR nanosheets are covered with CdS
nanoparticles completely. There is no apparent aggregation of
CdS nanoparticles on the GR scaold and no large areas of GR
without CdS decoration, which is consistent with the results of
SEM analysis and the previous reports.
48,65
The image of high-
resolution TEM (HRTEM) in Figure 3B shows distinct lattice
fringe of which the spacing is measured to be equal to 0.336 nm,
corresponding to the (111) crystal plane of hawleyite CdS. The
selected area electron diraction (SAED) pattern indicates that
the CdS5%GRnanocomposite possesses polycrystalline struc-
ture, which is in accordance with the result of XRD analysis. As
displayed in Figure 3C, the result of EDX gives the signals of C,
Cd, and S elements. Because the lacey support lm without
carbon coating is used, the signal of C must come from the GR
sheet in the nanocomposites, which further conrms the com-
position of the sample.
UVvis diuse reectance spectra (DRS) are used to deter-
mine the optical properties of the samples. It can be seen from
Figure 4A that the introduction of dierent weight contents of
GR has a signicant eect on the optical property of light
absorption for the as-prepared CdSGR nanocomposites. With
the increase of GR content, there is an enhanced absorbance in
the visible-light region ranging from 500 to 800 nm, which is in
accordance with the color change of the samples. A plot obtained
via the transformation based on the KubelkaMunk function
versus the energy of light is shown in Figure 4B. The estimated
band gap values of the samples are about 2.46, 2.43, 2.34, 2.33,
and 2.24 eV approximately, corresponding to blank-CdS,
CdS1% GR, CdS5% GR, CdS10% GR, and CdS30%
GR nanocomposites, respectively. This indicates a band gap
narrowing of the semiconductor CdS due to the introduction of
GR into the matrix of CdSGR nanocomposites. Such an
analogous phenomenon is also observed for other GR-based
semiconductor nanocomposites, which can be attributed to the
chemical bonding between semiconductor and graphene
support.
73
The photocatalytic activity of the as-prepared CdSGR
nanocomposites is initially examined by selective oxidation of
benzyl alcohol to benzaldehyde under visible light irradiation. As
Figure 4. UVvis diuse reectance spectra (DRS) of the samples of
blank-CdS and CdSGR nanocomposites with dierent weight addi-
tion ratios (A) and the plot of transformed KubelkaMunk function vs
the energy of light (B).
Figure 5. Photocatalytic selective oxidation of benzyl alcohol to ben-
zaldehyde under the visible light irradiation for 4 h over the as-prepared
samples: (a) blank-CdS; (b) CdS1% GR; (c) CdS5% GR; (d)
CdS10% GR; (e) CdS30% GR nanocomposites. Note: C & Y is
short for conversion and yield.
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ARTICLE
shown in Figure 5, when we take a viewof the overall activities, an
interesting trend is found. It can be seen that when a small
amount weight ratio of 1% GR is added, the selectivity to
benzaldehyde is enhanced while the conversion almost remains
the same as that for blank-CdS. When the weight ratio of GR is
increased to 5%, the optimal photocatalytic performance is
obtained, for which both the conversion and selectivity reach
the highest values in all the samples. Notably, the selectivity to
benzaldehyde is nearly 100%. Further increase of the GR weight
ratio in CdSGR leads to a deterioration of the photocatalytic
activity, which is also observed in other GR-based semiconductor
nanocomposites used for photocatalytic degradation of pollu-
tants and water splitting to hydrogen.
48,73
This is understandable
because relatively high weight ratio of GR in CdSGR nano-
composites would lower the contact surface of semiconductor
CdS nanoparticles with the light illumination,
73
thus leading to a
decreased photocatalytic activity, which accounts for the decline
in the conversion. In this case, there may be another important
reason for the drop in the selectivity. It is well-known that
a common feature of carbon species, such as zero-dimensional
ball-like fullerene (C
60
), one-dimensional carbon nanotubes
(CNTs), and two-dimensional graphene (GR), is their strong
adsorption capacity.
85,86
When the amount of GR in CdSGR is
relatively high, the target product aldehyde may not be easily
desorbed from the surface of photocatalysts due to the strong
adsorption ability of carbon species. In this case, further deep
oxidation of aldehyde may occur, thus leading to the decrease in
selectivity, as reected by the case of CdS10% GR and
CdS30% GR nanocomposites. Based on the above results,
the nanocomposite of CdS5% GR is chosen to evaluate the
photocatalytic activity for selective oxidation of other benzylic
and allylic alcohols.
Figure 6 lists the photocatalytic performance of selective
oxidation of a range of alcohols, including benzylic alcohols
and allylic alcohols over the photocatalyst of CdS5% GR and
blank-CdS under visible light irradiation. As can be clearly seen,
the CdS5% GR nanocomposite exhibits higher photoactivity
than blank-CdS in all selected reaction systems. The convers-
ion of alcohols increases gradually along the evolution of the
reaction. As for benzylic alcohols (Figure 6af), the yield of
Figure 6. Time-online photocatalytic selective oxidation of alcohols to aldehydes over blank-CdS and CdS5% GR nanocomposite under the
irradiation of visible light under ambient conditions: (a) benzyl alcohol; (b) p-methylbenzyl alcohol; (c) p-methoxybenzyl alcohol; (d) p-nitrobenzyl
alcohol; (e) p-uorobenzyl alcohol; (f) p-chlorobenzyl alcohol; (g) cinnamyl alcohol; (h) 3-methyl-2-buten-1-ol.
Figure 7. Photocatalytic selective oxidation of benzyl alcohol to ben-
zaldehyde over CdS5% GR nanocomposite under the irradiation of
visible light for 4 h in dierent solvents.
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corresponding benzylic aldehydes also rises with the reaction
progressing. However, for the case of allylic alcohols, such as
cinnamyl alcohol and 3-methyl-2-buten-1-ol (Figure 6gh), the
variation trend in yield is dierent from that of benzylic alcohols.
That is, the yield of target aldehydes does not increase with the
extension of irradiation time. This may be ascribed to double
bond cleavage of the allylic alcohols leading to no-growth
selectivity of the target aldehydes, which can be veried by the
results of GC/MS. The main byproducts generated in selective
oxidation of cinnamyl alcohol and 3-methyl-2-buten-1-ol are
proved to be benzaldehyde and acetone, respectively, both of
which result fromthe cleavage of CdCdouble bond in the allylic
alcohols. In addition, the eect of solvents has also been
investigated. As shown in Figure 7, taking selective oxidation of
benzyl alcohol to benzaldehyde as a testing reaction, it is found
that when nonuorinated solvents, such as toluene, acetonitrile,
and water, are used with other conditions unchanged, the conver-
sion of benzyl alcohol obtained over CdS5%GRnanocomposite
is lower than that in benzotriuoride. This can be ascribed to
the higher solubility for molecular oxygen of benzotriuoride.
1,2
The selectivity for benzaldehyde decreases with the increase in the
polarity of solvents, which may be due to the solvolysis of OO
bands in polar media.
87
To understand the role of GR in CdSGR nanocomposites
on enhancement of photoactivity, the surface area and porosity of
blank-CdS and CdS5%GRhave been investigated, as displayed
in Figure 8. It can be seen that the introduction of GR has an
eect on the pore structure of the samples. The nitrogen
adsorptiondesorption isotherm of blank-CdS exhibits type II
isotherm according to the IUPAC classication, which together
with the corresponding pore size distribution indicates the
nonporous structure.
88
The BET surface area of blank-CdS is
measured to be ca. 56 m
2
3
g
1
. The CdS5% GR nanocompo-
site has an adsorptiondesorption isotherm of type IV with a
typical H3 hysteresis loop characteristic of mesoporous solids,
which is conrmed by the corresponding pore size distribution as
shown in the inset of Figure 8. It is well-known that the type H3
loop is observed with aggregates of platelike particles giving rise
to slit-shaped pores.
88
That is, the as-prepared CdS5% GR
nanocomposite consists of GR nanosheets which are decorated
with CdS nanoparticles. The BET surface area of CdS5%GR is
ca. 57 m
2
3
g
1
, which is similar to that of blank-CdS. In addition,
adsorption experiments in the dark for alcohols have been
performed. As shown in Figure 9, the results suggest that there
is almost no dierence of adsorptivity between blank-CdS and
CdS5% GR. Therefore, the enhanced photocatalytic activity of
CdS5% GR nanocomposite compared with blank-CdS can not
be attributed to the change in surface area and porosity.
Figure 10 shows the transient photocurrent responses of
blank-CdS and CdS5% GR under intermittent visible light
illumination with the wavelength range used in the photocatalytic
reactions. It can be seen that the addition of GRis able to enhance
the photocurrent signicantly and the photocurrent rapidly
decreases to zero as long as the light is switched o. It is known
that the photocurrent is formed mainly by the diusion of the
photogenerated electrons to the back contact, and meanwhile the
photoinduced holes are taken up by the hole acceptor in the
electrolyte.
89
Therefore, the enhanced photocurrent over
CdS5% GR indicates a more ecient separation of the photo-
excited electronhole pairs and longer lifetime of the photo-
generated charge carriers as compared with blank-CdS. This
prolonged lifetime of the photogenerated charge carriers can also
be conrmed by the photoluminescence (PL) spectra. As
displayed in Figure 11, the PL intensity obtained over CdS5%
GR is much weaker than that of blank-CdS, thus suggesting the
Figure 8. BETadsorptiondesorption isotherms of blank-CdS (a) and
CdS5% GR nanocomposite (b); inset is the corresponding pore size
distribution.
Figure 9. Remaining fraction of various alcohols after the adsorp-
tiondesorption equilibrium is achieved over blank-CdS and CdS5%
GR nanocomposite: (a) benzyl alcohol; (b) p-methylbenzyl alcohol; (c)
p-methoxybenzyl alcohol; (d) p-nitrobenzyl alcohol; (e) p-uorobenzyl
alcohol; (f) p-chlorobenzyl alcohol; (g) cinnamyl alcohol; (h) 3-methyl-
2-buten-1-ol.
23508 dx.doi.org/10.1021/jp208661n |J. Phys. Chem. C 2011, 115, 2350123511
The Journal of Physical Chemistry C
ARTICLE
longer lifetime of photogenerated charge carriers. Similar nd-
ings are also reported in previous research works.
65,66
For
example, Cao et al.
65
found that GR could quench the uores-
cence of the CdS quantum dots decorated on it signicantly,
which can be attributed to the picoseconds ultrafast electron
transfer process from the excited CdS to the GR sheet.
In addition, other electrochemical analysis, including electro-
chemical impedance spectroscopy (EIS) Nyquist plots and
MottSchottky plot, has also been carried out. As shown in
Figure 12, the Nyquist plots of blank-CdS and CdS5% GR
electrode materials cycled in 0.1 M Na
2
SO
4
electrolyte solution
both show semicycles at high frequencies. Since the preparation
of the electrodes and electrolyte used are alike, the high-
frequency semicircles are related to the resistance of the
electrodes.
90
In electrochemical spectra, the high-frequency arc
corresponds to the charge transfer limiting process and can be
attributed to the double-layer capacitance (C
dl
) in parallel with
the charge transfer resistance (R
ct
) at the contact interface
between electrode and electrolyte solution.
91,92
It can be clearly
seen from Figure 13 that the introduction of GR leads to
dramatic decrease of the arc as compared to blank-CdS, suggest-
ing that GR can facilitate the interfacial charge transfer.
90
Figure 14 exhibits the MottSchottky plot for CdS5% GR.
The positive slope of the C
2
E plot suggests the expected
n-type semiconductor of CdS in the nanocomposite.
93
The at-
band potential (V
fb
) obtained by extrapolation of the Mott
Schottky plot approximately equals 0.69 V vs Ag/AgCl, 0.49 V
vs NHE,
94
which is more negative than the standard reduction
Figure 10. Transient photocurrent response of blank-CdS and
CdS5% GR nanocomposite in 0.2 M Na
2
SO
4
aqueous solution
without bias versus Ag/AgCl under the irradiation of visible light.
Figure 11. Photoluminescence (PL) spectra of blank-CdS and
CdS5% GR nanocomposite.
Figure 12. Nyquist impedance plots of blank-CdS and CdS5% GR
nanocomposite.
Figure 13. MottSchottky plot for the CdS5% GR nanocomposite
in 0.2 M Na
2
SO
4
aqueous solution (pH = 6.8).
Figure 14. ESR spectra of radical adduct trapped by DMPO
(DMPOO
2

) over the CdS5% GR nanocomposite suspension in


the BTF solution without or with the visible light irradiation.
23509 dx.doi.org/10.1021/jp208661n |J. Phys. Chem. C 2011, 115, 2350123511
The Journal of Physical Chemistry C
ARTICLE
potential of oxygen (0.15 V vs NHE).
1
Therefore, it is thermo-
dynamically permissible for the transformation of photogener-
ated electrons to the absorbed O
2
to produce the superoxide
radicals (
3
O
2

), which is faithfully veried by the electron spin


resonance (ESR) spectra, as shown in Figure 14. Notably, strong
and nonselective hydroxyl radicals
1,17
are not detected by the
ESR analysis. Accordingly, a possible mechanism for photocata-
lytic selective oxidation of alcohols over CdSGRis proposed, as
illustrated in Figure 15. Under visible light irradiation, the
electron is excited from valence band (VB) of CdS nanoparticles
to its conduction band (CB), leaving the hole in the VB. The
photoinduced electrons transfer to GR because of the excellent
intimate contact between CdS and GR, which hinders the
recombination of electrons and holes eciently. The adsorbed
alcohol can be oxidized by the hole to produce alcohol radical
cation, which reacts with molecular oxygen or superoxide radicals
to give the target product aldehyde.
17
Thus far, based on the above discussion, the primary role of
addition of an appropriate amount of GR in the CdSGR
nanocomposite can be summarized as follows. (1) The visible
light absorption intensity is improved due to the introduction of
GR. (2) The lifetime of photogenerated electronhole pairs is
prolonged signicantly because GR serves as an electron accep-
tor and transporter. (3) GR is able to control the morphology of
the as-prepared CdSGR nanocomposites during the synthesis
process. We think that these integrative factors account for the
observation of enhanced photoactivity of CdS5% GR as
compared to blank-CdS toward visible light photocatalytic
selective oxidation of alcohols under ambient conditions.
4. CONCLUDING REMARKS
In summary, a series of CdSGR nanocomposites with
dierent weight addition ratios of GR have been fabricated via
a facile one-step approach during which the formation of CdS
nanoparticles and the reduction of GO occur simultaneously. In
the synthesis process, GR nanosheet can function as a two-
dimensional scaold for the CdS nanoparticles to evenly over-
spread on it. The introduction of GR has a signicant eect on
the properties of the samples, including morphology, optical,
and electronic nature as compared with blank-CdS. Our results
demonstrate that the as-prepared CdSGR nanocomposites are
able to serve as a promising visible-light-driven photocatalyst for
selective oxidation of alcohols to corresponding aldehydes under
mild conditions. The high photoactivity of CdSGR nanocom-
posites can be attributed to the integrative eect of the enhanced
light absorption intensity, high electron conductivity of GR, and
its signicant inuence on the morphology and structure of the
samples. To our best knowledge, it is the rst time to utilize
CdSGR nanocomposites as visible light photocatalyst for
selective organic synthesis. It is expected that our current work
could open the doorway for the exploration on GRCdS and
other GR-based semiconductor nanocomposites for visible-light-
driven photocatalytic selective organic transformations.
AUTHOR INFORMATION
Corresponding Author
*Tel. /fax +86 591 83779326; e-mail yjxu@fzu.edu.cn.
ACKNOWLEDGMENT
The support by the Award Program for Minjiang Scholar
Professorship, the National Natural Science Foundation of
China (20903023, 21173045), Program for Changjiang Scholars
and Innovative Research Team in Universities (PCSIRT0818),
National Basic Research Program of China (973 Program:
2007CB613306), Program for Returned High-Level Overseas
Chinese Scholars of Fujian province, and the Project Sponsored
by the Scientic Research Foundation for the Returned Overseas
Chinese Scholars, State Education Ministry, is gratefully
acknowledged.
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