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29 views8 pagesGC 3 N 4
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/ 8
ROYAL SOCETY
SethenistaY
RSC Advances
NUECES
Facile synthesis of g-C;N, nanosheets loaded with
WO; nanoparticles with enhanced photocatalytic
performance under visible light irradiation}
check tor updates
Ce ts ASC At, 2007, 7, 24087
Jie Meng, @® Jingyuan Pe, Zefang He, Shiyan Wu, Gingyun Lin, xiao Wel* Jue Li
dnd Ze Zhang
Graphite carbon nitvide (g-CsN.) nanosheets loaded with WO; nanoparticles were prepared va heat
‘weatment of g-C.Ns together with WO,-EDA nanobelts. The thermal treatment temperature and WO,-
EDA precursor play the key role in enhancing the inceraction between WOs nanoparticles and g-CsNy
rnanosneets, because the temperature of thermal decomposttion of WO,-FDA (~400 °C} is close to te
thermal exfolation temperature of g-CsNs. The structure evolution and promotion tect of te
nanocomposites in ghotocatairic performance were well studied, It found that WOy nanoparticles
Unformily dispersed on the surface of the g-C.N nanosheets, andthe close integration of WO; and g-
CiNs lead to the high photocataiytic activity in the degradation of Rh Under visible Light iradation,
Meanwhile, a larger specif area and increase of visible light absorption are also of bereft to speed up
the degradation of organic dye. Also, the mechanism of the photocatalytic reaction and its reutlization,
Received 24th February 2057
‘Accepted 25th Nor 2017
bor: 101039/¢79022970
‘Open Access Article, Published on 03 May 2017. Downloaded on 0605/2017 17:12:11.
(KESNSEMMMNMN Tisai icensd under a Creative Commons Atibution 3.0 Unporieé Licence,
rselise-advances properies were investigates.
Introduction
Photocatalysts have been receiving much attention as a prom:
ising material in recent years due to their applications in alle
ing global environmental pollution and the energy crisis,
such as waste pollutant degradation, water splitting? and CO,
reduction.* However, there are some major challenges that
hamper the requirements of their practical applications, for
Instance, a high recombination rate of photorexcited charge
carciers, low solar energy conversion efficiency resulting from
a wide band gap, and other restrictions ** Accordingly, it is
essential to develop a high performance photocatalyst that
could not only enhance the separation and transportation ef
ciency of electron-hole pairs but also improve the light
absorption properties under solar radiation,
Graphitic carbon nitride (g-C,N,), a great potential material
for photocatalytic reaction first reported by Wang etal. in early
2009,” has received intensive attention on account ofits unique
electronic and optical properties, such as visible light response,
{good reduction ability, easy synthesis, and high stabilities,
‘What's more, the band gap of g-C,N, is around 2.7 eV, which
could absorb visible light up to 460 nm correspondingly** The
Gener of lecon Miroscopy, ute Key Laboratory of Sn Materials Sco of
Materate Sense and Enginerng, Zing Universi, Hanghow, #1027, PR
China Rima mueweaogu ech, Fax: +85 571 $7989797; Tel +46 571
1 Blezonle supplementary
Infomation
sy
swale, see DOE
conduction band edge potential of g-CNy is more negative
{about —1.12 eV vs, NEE), therefore, photoinduced electrons
would have high reduction capacity." Nevertheless, it has
‘been concluded thatthe low phatocatalytic activites of g-C,Ny
aze mainly atrbuted to high recombination of photogenerated
charge cattiers and low specific surface area™* Many efforts
hhave Been made to overcome these bottlenecks. It was reported
that ulvasonie vibration," thermal exfoliation and hydro-
thermal treatment” could be used to change the BEI surface
aca, Meanwhile, doping," noble metal loading" and coupling,
With other semiconductors? are also etfetive methods to ach-
ieve the separation of carters and then farther increase the
Photocatalytic performance under visible light illumination
Amongall the strategies, coupling with other semiconductors is
an efficient attempt to solve abave two questions due to the
suitable band position and enhanced hole-eleetron_pairs
transfer between the two semiconductors by appropriate
combination syle. Fspecialy, x-C,Ny nanoshects which show
distinct physical and chemical features with larger specific stea
and outstanding electronic mobility,
appropriate candidate to couple with other semiconductors to
form high-performance photocatalysts. As a matter of fact,
‘many progresses have been made on g-C,N, nanosheets based
composites,» such as TiOalg-C.Ng2" Z001g-C,Nq* Bi,WOdlg-
GN? MoSs/g-CNai* ete. These composite systems have
deservedly achieved enhanced photocatalytic performance
which is generally ascribed to the improved reaction sites,
charge separation and migration processes. Nevertheless, i is
necessary for a practical photocatalyst to be provided with
sre considered to be an
ASC Aa, 20077, 24087-20904 | 24087 “Theale cent under @ Creative Commons Atnbution 3.0 Unported Licence,
‘Open Access Article, Published on 03 May 2017. Downloaded on 06/05/2017 17:12:11.
3)
RSC Advances
stable crystal structure, narrow band gap, low material cost, and
easy preparation. So there is still a long way to seck a proper
‘material coupling with g-CyN, nanosheets to form highly active
composite photocatalyss
‘Alternatively, tungsten(v) oxide (WO,) which is deemed as
« promising material of photocatalysts™ with a narrow band gap
of about 2.7 eV, i a potential candidate to form composites with
OWN, nanosheets to get excellent photocatalytic performance.
Meanwhile, its stable crystal structure, resistance to photo
corrosion, and inexpensiveness are all important issues for the
practical application" The VB edge potential of WO, is more
positive, implying chat it has a better oxidation capability in
photocatalytic activities. However, the CB position of WO, limits
its photocatalytic reaction under visible light illumination since
this CH level is not beneficial to the single-lectron reaction of
(0,2 Ic could decrease the recombination of hole-electton pairs
and make up the defects of the conduction band by synergistic
effect of two semiconductors when WO coupling with g-O3N,"™
‘Therefore, WO, is a proper candidate to form composites with g-
G.Ny to achieve excellent photocatalytic performance under
visible light imradiation, However, for photocatalytic composites,
the separation efficiency of photo-induced carters is: not only
related to appropriate electronic structures, but most importantly
determined by effective combination with better contact, that is
still a challenge for most semiconductor composites. Many
attempts have been applied to form WOs/g-C,N, composites to
achieve the above goals, but there are no reports about using the
'WO,-EDA nanobelts, asthe precursor of WO, to synthesize WO,/
EOAN, composites with a suitable combination method which
could not only enlarge the specific surface area but also restrain
jon of photo-xcited carriers2~” The WO-EDA
nanobelts was synthesized by solvothermally treating WO, in
cthanediamine (EDA) following a soalled solventcoordination
molecular template (SCMT) mechanism."
In this paper, we prepared the WOs/eCN, composites
through heat teatment of WO,EDA and C,Ny. Since the
decomposition temperature (around 400 °C) of WO,-EDA is close
to thermal exfoliation temperature of g-C,Na, both of two reac
tion processes conduct simultaneous, which was found to faci
Hate WO, nanoparticles to uniformly disperse on g-C,N,
nnanosheets. The photocatalytic performance of the WOs/g-C,N,
composites was evaluated by the degradation of Rhodamine B
under visible light illumination, The dectease of recombination
of photo-generated hole-electron pairs evaluated by photo
uminescence (PL) spectra, larger specifi surface area calelated
by BET method and enhanced visible light absorption charac
terized by diffuse reflectance spectrum (DRS} are main reasons to
increase photocatalytic activity. Based on the systematically
characterizations of the photocatalyst, a possible mechanism
for the enhanced photocatalytic performance of WOs/g-C.Ns
composites is proposed.
the recombin:
Experimental section
Materials and synthesis
Al of the chemical reagents used in this experiment were of
analytical stage without further purification,
24098 | HSC Ade, 20177, 24087-20104
Paper
Pristine g-C,Na synthesis, Pristine g-C,N, was prepared by
directly heating melamine in mutfle furnace.” In a (ypical
procedure, melamine powder was put into alumina crucible
with a cover, then heated to 550 °C for 4 h at a heating rate of
3.5 °C min” after cooling to room temperature in the way of
arnace cooling, the yellow powder was ground and collected for
subsequent use.
WO-EDA synthesis. The WO,-EDA was synthesized by sok
vothermal treatment of m-WO, (monoclinic WO,), and m-WO,
was prepared by hydrothermal route, Firstly, 10 mmol Na;
WO, -2H,0 was dissolved in distilled water (40 ml}, then 5 mL.
of HINO, was added into aqueous solution under stirring at
oom temperature. After sticting for about 1 h, the mixture was
transferred into a 50 mL Teflon-lined stainless-steel autoclave,
heated to 200 °C for 48 hand then cooled to room temperature
naturally. The yellow product, named m-WO,, was washed,
dried, ground and collected for next use. Secondly, WO,-FDA
was prepared according to previous report similarly." Typically,
1 gof as-prepared m-WO, powder and 40 mI. of ethanediamine
(EDA) were mixed under stirring for 60 min. The mixture was
heated to 200 °C for 12 h by solvothermal treatment. After
cooling to room temperature, the product was collected after
washed, dried and ground for subsequent use, namely WO
EDA (Fig. Si).
WO,ig-CsN, composites synthesis. Typically, 0.4 g WO EDA
and 1 g pristine g-C.N, were mixed in ethanol solution under
ultrasonication for 1 h, and then dried at $0 °C for about 12h.
(ig. S2f) The obtained mixture was annealed to 400 °€ for 2 h,
and the final sample is called WECNAO, According to different
mass ratio between WO;EDA and $-0,N,, the samples are
named CN oF §-CNe, WECN20, WECNS0, WECNSO, WECNSO
and WO, (Scheme 1). All above six samples were prepared using.
the same treating process as same as WECN4O,
Characterization
‘The crystalline phases of the as-synthesized samples were
characterized by X-tay diffraction (XRD, PANalytical XPert PRO}
with Cu K radiation with 26 from 10-80". The morphology and
composition of the as-obtained samples were investigated by
field emission scanning electron microscopy (SEM, Hitachi SU-
70) and transmission electron microscopy (TEM, FEI Tecnai G*
20 S-TWIN) equipped with an energy dispersive X-ray spec
trometer (EDX). Specific surface area (Sye:) was determined
with a surface area anslyser (Quantachrome AUTOSORE-IQ2-
MP) by the BET method. Diffuse reflectance spectra (DRS) was
measured by a UV-vis spectrophotometer (Persee TU-1900)
Scheme 2 Schematic presentation of the synthesis process of
WOs/9-CsNa composites. ‘Open Access Article, Published on 03 May 2017. Downloaded on 06/05/2017 17:12:11.
(KESNSEMMIMN This rite is cened under «Creative Commons Attribution 3.0 Uaprid Licence
Paper
equipped with an integrating sphere unit using BaSO, as the
reflectance standard. Photoluminescence (PL) spectra was ob-
tained by fluorescence spectrometer (Edinburgh instruments
FLS920), Fourier transform infrared (FTIR) spectra of samples
was recorded using a Nicolet Avatar-370 spectrometer at room,
temperature. The surface electronic states of the samples were
measured by X-ray photoelectron spectroscopy (XPS, Escalab
250Xi). The concentration of phenol was characterized by liquid
chromatograph (C1#-005 column).
Photocatalytic measurement
‘The photocatalytic performances of the WO,/CN samples were
characterization by the degradation of Rhodamine B (Rh)
under visible light. A 300 W xenon lamp acts as a visible light
source equipped with a UV cutoff fier (2 > 420 nm) dusing the
experiment, For photocatalytic test, 0.05 g of the photocatalyst
was dissolved in 100 mt. of 10 mg L~* RMB solution in glass
beaker, Before tradition, the solution was magnetically sized
in the dark for 30 minutes to achieve adsorption 420 nm) served as light source in the
photocurrent tests obtained at 0.5 Vv. AgiigCl
Results and discussion
Characterization of WOs/g-C:N, composites
Fig. 1 shows the XRD patterns of g-C,Ny, WO, and serials WO,/
EC.N, composite photocatalysts. It is observed that two
difraction peaks areas around 27.7" and 12.9" for g-C.Ny
GePDS 87-1526), are corresponding to che (002) and (100)
diffraction planes, respectively. According to the reported
results, the stronger peak at 27.7" corresponds to the inter
layer stacking of the aromatic systems with the interlayer
distance of 0.322 nm. The weaker one at 129° which attributes
toa distance around d = 0.686 nm is related to in-plane tris
RSC Advances
eros
Intensity (au)
Degree (2 Theta)
fig. 1 XRD pattems of g-CsNy, WOs and WOs!g-CsNe composite
photocataysts
tuazine structural packing. For WOy, it can be index to the
monoclinic structure JCPDS card no, £40950 with latice
parameters of @ = 7.201 4, 6 = 7.529, ¢=7.690 A and a ==
90°, = 90,892") and the main difftaetion peaks 3¢23.3°,23.7°
245°, 267°, 288°, 343°, 41.7", 500", and 55.94" are corre-
sponding to (002), (020), (200), (120), (112), (202), (222), (400),
and (420) planes, respectively. For WO,/g-C,N, composites, the
XRD patterns revel a coexistence of WO, and -C:Ny. The
intensity of characteristic (002) peak assigned to g-CyNy
becomes weaker with the increasing WO, content in the
composites gradually, The (100) peak ascribed to g-C,Ng is not
‘observed inthe composites which may be duc tothe relative low
intensity compared to WO, The main peak changes slightly
compared to original 27.7" for g-CsN, resulted from the intro-
