Beruflich Dokumente
Kultur Dokumente
a r t i c l e i n f o a b s t r a c t
Article history: Bi2WO6 is incorporated on graphene sheets using a facile reuxing method to improve its photocatalytic
Received 4 October 2011 performance. Remarkable three times enhancement in photodegradation of Rh.B is observed on Bi2WO6/
Received in revised form 17 October 2011 graphene composite compared with pure Bi2WO6 under visible light irradiation. This improvement is
Accepted 20 October 2011
attributed to the longer electron lifetime of excited Bi2WO6 as the electrons even if holes are injected
Available online 26 October 2011
to graphene instantly at the site of generation, leading to a maximized charge separation. This study dem-
onstrated that the graphene as supporter could provide an effective way for enhancing photocatalytic
Keywords:
performance of semiconductor photocatalysts by acting as charge transfer channel.
Graphene sheets
Visible light
2011 Elsevier B.V. All rights reserved.
Photocatalytic activity
Charge transfer
1383-5866/$ - see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2011.10.025
Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105 99
function of irradiation time from the absorbance region at a wave- images of the Bi2WO6/graphene (Fig. 2c) and the corresponding
length line of 555 nm. elemental mapping (Fig. 2df) show homogeneous distribution of
C, Bi and W in the entire range.
To better study the interface structure between the two phases,
3. Results and discussion
the Bi2WO6/graphene was further examined with high-resolution
transmission electron microscopy (HR-TEM). The well-crystallized
3.1. Surface characteristics and element analysis
structure with lattice spacing of 0.223 nm corresponds to the
(1 0 1) planes of the orthorhombic Bi2WO6 (Fig. 3a), It can be fur-
The tapping mode AFM image (Fig. 1) of GO shows macro size
ther seen from Fig. 3b that the graphene sheet with the basal plane
sheets and the height prole of thickness indicates formation of
is perfectly bridged with Bi2WO6. For comparison, the Bi2WO6/CNT
single layer GO.
was synthesized using similar reuxing method and TEM image of
The structure of Bi2WO6/graphene is investigated by TEM. The
Bi2WO6/CNT indicates that a separated phases of Bi2WO6 and CNT
2D graphene sheets and Bi2WO6 nanoparticles are clearly observed
(Fig. S-3). Most recently, Xu et al. reported a systematic compari-
in Fig. 2a. Bi2WO6 nanoparticles are randomly distributed on the
son study between graphene/TiO2 photocatalysts and their ana-
surface and edges of the graphene sheets, which is further con-
logues CNTTiO2 [25], which demonstrated that the role of
rmed by SEM images (Fig. S-2). TEM image of Bi2WO6/graphene
graphene is much the same way as its carbon forebears. Subse-
in Fig. 1b shows irregular Bi2WO6 nanoparticles containing square
quently, the authors claimed that full and intimate coverage of
Bi2WO6 nanoplates. The square nanoplates can be attributed to
the individual 2D sheet of graphene with TiO2 can maximize the
anisotropic growth in the crystalline-ripened process. The STEM
Fig. 2. The TEM images (a and b), STEM image (c) and elemental mapping images (df) of Bi2WO6/graphene.
Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105 101
Fig. 4. (a) The XRD patterns and FT-IR spectra of GO, Bi2WO6 and Bi2WO6/graphene. (c) The Raman spectra of GO and Bi2WO6/graphene and (d) the UVvis diffuses
reectance spectra of Bi2WO6 and Bi2WO6/graphene.
excellent electron conductivity of graphene [26]. Because the supe- of the GO corresponds to the layer-to-layer distance (d-spacing) of
rior and easily accessible structure directing role of GO (the pre- 0.78 nm. All the peaks for the Bi2WO6 are readily indexed to the
cursor of graphene) in an aqueous phase is able to be utilized easy orthorhombic phase of Bi2WO6 (JCPDS card no. 73-1126). It is also
and sufciently compared to CNT. As a result, the GO as starting found that the main diffraction peaks of Bi2WO6/graphene are sim-
materials can promote interaction of Bi2WO6 and GO through ilar to that of pure Bi2WO6. No obvious diffraction peak attribute to
physisorption, electrostatic binding or through charge transfer GO or graphene is observed, which suggests that low content and
[27]. the stacking of the graphene sheets disordered.
The FT-IR spectra of GO, Bi2WO6, and Bi2WO6/graphene are
3.2. Crystal and optical properties shown in Fig 4b. The representative absorption peaks of GO includ-
ing those at 3400 cm1 (OH stretching vibration), 1736 cm1
The XRD patterns of GO, Bi2WO6, and Bi2WO6/graphene are (C@O stretching vibration of COOH groups), 1396 cm1 (tertiary
shown in Fig 4a. The diffraction peak at 10.45 in the XRD pattern COH stretching vibration), and 1072 cm1 (CO stretching vibra-
102 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105
Fig. 6. Photocurrent transient responses of Bi2WO6 and Bi2WO6/graphene under The photocatalytic degradation of Rh.B under visible light irra-
visible light irradiation. diation is utilized to evaluate the photocatalytic performance of
the Bi2WO6/graphene, as shown in Fig. 7. It can be seen that Rh.B
tion), are in good agreement with previous work [28]. The Bi2WO6 is very stable under visible light irradiation without any catalyst
has main absorption peaks between 500 and 1200 cm1, which can or in the presence of graphene sheets in Fig. 7a. The degradation
be attributed to stretching vibration of BiO and WO, and bending of Rh.B can be obviously occurred over Bi2WO6, mixed Bi2WO6
vibration of WOW [29,30]. Obvious decreases in intensity or and graphene, and 5 wt.% Bi2WO6/graphene, suggesting the excita-
even disappearance after solvothermal reduction in FT-IR spec- tion of the Bi2WO6 under visible light, and the Bi2WO6 and 5 wt.%
trum of Bi2WO6/graphene indicate that the oxygen-containing Bi2WO6/graphene can be greatly dispersed in Rh.B solution before
functional groups in GO are decomposed in the solvothermal envi- and after visible light irradiation (Fig. S-4). The mixture of graph-
ronment [31]. The absorption band appearing at 1689 cm1 clearly ene and Bi2WO6 shows slightly higher photocatalytic activity than
shows the skeletal vibration of the graphene sheets, indicating the that of pure Bi2WO6. It has been found that the 5 wt.% Bi2WO6/
formation of graphene in Bi2WO6/graphene. graphene exhibit higher photocatalytic activities than Bi2WO6
Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105 103
Fig. 7. (a) Photocatalytic degradation of Rh.B under visible light (k > 420 nm) as a function of irradiation time by the graphene, Bi2WO6, mixture of Bi2WO6 and graphene, and
5 wt.% Bi2WO6/graphene. (b) The kinetics of photocatalytic degradation of Rh.B by the Bi2WO6 and 5 wt.% Bi2WO6/graphene. (c) Photocatalytic degradation of Rh.B under
visible light (k > 420 nm) as a function of irradiation time by the Bi2WO6 and 5 wt.% Bi2WO6/graphene in presence of H2O2 (2 105 M). (d) Photocatalytic degradation
efciencies of Rh.B under visible light (k > 420 nm) as a function of irradiation time by the Ag2WO4, 5 wt.% Ag2WO4/graphene, BiVO4, 5 wt.% BiVO4/graphene, CdS, and 5 wt.%
CdS/graphene.
and mixture of graphene and Bi2WO6 both. The pseudo-rst-order in an effective separation of photogenerated electron/hole pairs
kinetics of photocatalytic degradation ratio for the Bi2WO6 and and fast interfacial charge transfer to the electron donor/electron
5 wt.% Bi2WO6/graphene in Fig. 7b show that the Bi2WO6/graphene acceptor. To further verify the electron transfer by graphene sup-
is about three times greater than Bi2WO6. Previous study had dem- porter, more semiconductor photocatalysts, such as Ag2WO4,
onstrated that direct hole oxidation and O 2 oxidation reaction BiVO4 and CdS combined with graphene in 5 wt.% content are syn-
mainly govern the photocatalytic process by adding holes and hy- thesized for degradation of Rh.B. Synthesis route is similar to
droxyl radicals scavengers in graphene/semiconductors system Bi2WO6/graphene in an EG solvent by a hydrothermal reaction,
[21,36]. Herein, addition of H2O2 as electron accepting agents is their FT-IR, XRD and UVvis DRS analysis show true composites
used to evaluate effective separation of electron/hole pairs in pres- with obvious visible light response (Fig. S-5). As shown in Fig. 7d,
ence of graphene sheets, the effect on the degradation kinetics of all graphene based semiconductor photocatalysts show 23 times
Rh.B is illustrated in Fig. 7c. It is obvious that the degradation rate greater than individual semiconductor in photocatalytic perfor-
of Rh.B on 5 wt.% Bi2WO6/graphene is accelerated. However, on mances. It suggests that the graphene sheets as charge transfer
pure Bi2WO6, degradation of Rh.B is slightly slower in the presence channel can effectively transfer electrons, even holes for semicon-
of H2O2. It can be considered that the OH radical formation on ductor with different band gaps.
Bi2WO6 in presence of H2O2 can be decreased by the process of Degradation of Rh.B are further carried out for 120 wt.% graph-
recombination of holes, which is formed on Bi2WO6 surface after ene supported Bi2WO6 to optimize graphene loading in Bi2WO6.
its excitation with electrons due to supplying H2O2 [37]. The differ- The photocatalytic performances enhance in the degradation of
ent behavior of degradation of Rh.B on Bi2WO6/graphene can be Rh.B up to 5 wt.% graphene loading, after which it starts decreasing
supposed to prior adsorbed H2O2 on the graphene surface, there- (Fig. 8a). It can be deduced that the gap of degradation perfor-
fore the amounts of OH radical formed main due to reacted with mance among Bi2WO6/graphene with different graphene contents
transferred electrons is higher on Bi2WO6/graphene. Additionally is mainly related to weakening photon absorption ability, which
OH radical formation on the surface of Bi2WO6 is suppressed by have been conrmed in graphene based photocatalysts by previous
the scavenging of the free carriers by H2O2. Based on the above re- reports [36,38]. After conrming the fact that graphene supported
sults, the photocatalytic activity enhancement can be attributed to Bi2WO6 should serve as an advanced photocatalyst that assists the
the introduction of graphene as charge transfer channel, resulting charge separation, the degradation of Rh.B also indicates if
104 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105
4. Conclusions
Acknowledgements
References
[6] L.S. Zhang, W.Z. Wang, Z.G. Chen, L. Zhou, H.L. Xu, W. Zhu, Fabrication of [23] M.J. Allen, V.C. Tung, R.B. Kaner, Honeycomb carbon: a review of graphene,
ower-like Bi2WO6 superstructures as high performance visible-light driven Chem. Rev. 110 (2010) 132145.
photocatalysts, J. Mater. Chem. 24 (2007) 25262532. [24] W. Hummers, R. Offeman, Preparation of graphitic oxide, J. Am. Chem. Soc. 80
[7] J. Wu, F. Duan, Y. Zheng, Y. Xie, Synthesis of Bi2WO6 nanoplate-built (1958) 1339.
hierarchical nest-like structures with visible-light-induced photocatalytic [25] Y. Zhang, Z.R. Tang, X. Fu, Y.J. Xu, TiO2-graphene nanocomposites for gas-phase
activity, J. Phys. Chem. C 111 (2007) 1286612871. photocatalytic degradation of volatile aromatic pollutant: is TiO2-graphene
[8] J.Q. Yu, A. Kudo, Effects of structural variation on the photocatalytic truly different from other TiO2-carbon composite materials?, ACS Nano 4
performance of hydrothermally synthesized BiVO4, Adv. Funct. Mater. 16 (2010) 73037314.
(2006) 21632169. [26] Y. Zhang, Z.R. Tang, X. Fu, Y.J. Xu, Engineering the unique 2D mat of graphene
[9] L. Ren, L.L. Ma, L. Jin, J.B. Wang, M.Q. Qiu, Y. Yu, Template-free synthesis of to achieve graphene-TiO2 nanocomposite for photocatalytic selective
BiVO4 nanostructures: II. Relationship between various microstructures for transformation: what advantage does graphene have over its forebear
monoclinic BiVO4 and their photocatalytic activity for the degradation of carbon nanotube?, ACS Nano 5 (2011) 74267435.
rhodamine B under visible light, Nanotechnology 20 (2009) 405602405611. [27] A.V. Moholkar, S.M. Pawar, K.Y. Rajpure, Saleh N. Almari, P.S. Patil, C.H.
[10] W.C. Oh, F.J. Zhang, Z.D. Meng, K. Zhang, Relative photonic properties of Fe/ Bhosale, Solvent-dependent growth of sprayed FTO thin lms with mat-like
TiO2-nanocarbon catalysts for degradation of MB solution under visible light, morphology, Sol. Energy Mater. Sol. Cells 92 (2008) 14391444.
Bull. Korean Chem. Soc. 31 (2010) 11281134. [28] J.I. Paredes, S. Villar-Rodil, A. Martinez-Alonso, J.M.D. Tascon, Graphene oxide
[11] N. Bouazza, M. Ouzzine, M.A. Lillo-Rdenas, D. Eder, A. Linares-Solano, TiO2 dispersions in organic solvents, Langmuir 24 (2008) 1056010564.
nanotubes and CNTTiO2 hybrid materials for the photocatalytic oxidation of [29] D.K. Ma, S.M. Huang, W.X. Chen, S.W. Hu, F.F. Shi, K.L. Fan, Self-assembled
propene at low concentration, Appl. Catal. B: Environ. 92 (2009) 377383. three-dimensional hierarchical umbilicate Bi2WO6 microspheres from
[12] W. Zhou, K. Pan, Y. Qu, F.F. Sun, C.G. Tian, Z.Y. Ren, G.H. Tian, H.G. Fu, nanoplates: controlled synthesis, photocatalytic activities, and wettability, J.
Photodegradation of organic contamination in wastewaters by bonding TiO2/ Phys. Chem. C 113 (2009) 43694374.
single-walled carbon nanotube composites with enhanced photocatalytic [30] L.H.M. Krings, W. Talen, Wet chemical preparation and characterization of
activity, Chemosphere 81 (2010) 555561. electrochromic WO3, Sol. Energy Mater. Sol. C 54 (1998) 2737.
[13] Tawk A. Saleh, M.A. Gondal, Q.A. Drmosh, Z.H. Yamani, A. AL-yamani, [31] A.V. Murugan, T. Muraliganth, A. Manthiram, Facile microwave-solvothermal
Enhancement in photocatalytic activity for acetaldehyde removal by synthesis of graphene nanosheets and their polyaniline nanocomposites for
embedding ZnO nano particles on multiwall carbon nanotubes, Chem. Eng. J. energy storage, Chem. Mater. 21 (2009) 50045006.
166 (2011) 407412. [32] J. Zhang, H. Yang, G. Shen, P. Cheng, J. Zhang, S. Guo, Reduction of graphene
[14] C. Martnez, M. Canle L, M.I. Fernndez, J.A. Santaballa, J. Faria, Kinetics and oxide via L-ascorbic acid, Chem. Commun. 46 (2010) 11121114.
mechanism of aqueous degradation of carbamazepine by heterogeneous [33] L.W. Zhang, H.B. Fu, Y.F. Zhu, Efcient TiO2 photocatalysts from surface
photocatalysis using nanocrystalline TiO2, ZnO and multi-walled carbon hybridization of TiO2 particles with graphite-like carbon, Adv. Funct. Mater. 18
nanotubes-anatase composites, Appl. Catal. B: Environ. 102 (2011) 563571. (2008) 21802189.
[15] O. Akhavan, M. Abdolahad, Y. Abdi, S. Mohajerzadeh, Synthesis of titania/ [34] P. Wang, T.F. Jiang, C.Z. Zhu, Y.M. Zhai, D.J. Wang, S.J. Dong, One-step,
carbon nanotube heterojunction arrays for photoinactivation of E. coli in solvothermal synthesis of graphene-CdS and graphene-ZnS quantum dot
visible light irradiation, Carbon 47 (2009) 32803287. nanocomposites and their interesting photovoltaic properties, Nano Res. 3
[16] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V. (2010) 794799.
Grigorieva, A.A. Firsov, Electric eld effect in atomically thin carbon lms, [35] X. Wang, L.J. Zhi, K. Mullen, Transparent, conductive graphene electrodes for
Science 306 (2004) 666669. dye-sensitized solar cells, Nano Lett. 8 (2008) 323327.
[17] A.K. Geim, K.S. Novoselov, The rise of graphene, Nat. Mater. 6 (2007) 183191. [36] T.G. Xu, L.W. Zhang, H.Y. Cheng, Y.F. Zhu, Signicantly enhanced photocatalytic
[18] S. Park, R.S. Ruoff, Chemical methods for the production of graphenes, Nat. performance of ZnO via graphene hybridization and the mechanism study,
Nanotechnol. 4 (2009) 217224. Appl. Catal. B: Environ. 101 (2011) 382387.
[19] Y.H. Ng, A. Iwase, A. Kudo, R. Amal, Reducing graphene oxide on a visible-light [37] B. Tryba, A.W. Morawski, M. Inagaki, M. Toyoda, The kinetics of phenol
BiVO4 photocatalyst for an enhanced photoelectrochemical water splitting, J. decomposition under UV irradiation with and without H2O2 on TiO2, Fe
Phys. Chem. Lett. 1 (2010) 26072612. TiO2 and FeCTiO2 photocatalysts, Appl. Catal. B: Environ. 63 (2006) 215
[20] E.P. Gao, W.Z. Wang, M. Shang, J.H. Xu, Synthesis and enhanced photocatalytic 221.
performance of graphene-Bi2WO6 composite, Phys. Chem. Chem. Phys. 13 [38] T.G. Xu, L.W. Zhang, H.Y. Cheng, Y.F. Zhu, Appl. Catal. B: Environ. 101 (2011)
(2011) 28872893. 382387.
[21] X.F. Zhang, X. Quan, S. Chen, H.T. Yu, Constructing graphene/InNbO4 composite [39] D. Wang, D. Choi, J. Li, Z. Yang, Z. Nie, R. Kou, D. Hu, C. Wang, L.V. Saraf, J. Zhang,
with excellent adsorptivity and charge separation performance for enhanced I.A. Aksay, J. Liu, Self-assembled TiO2-graphene hybrid nanostructures for
visible-light-driven photocatalytic ability, Appl. Catal. B: Environ. 105 (2011) enhanced Li-ion insertion, ACS Nano. 3 (2009) 907914.
237242. [40] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, M.I. Katsnelson, I.V.
[22] G. Williams, B. Seger, P.V. Kamat, TiO2-graphene nanocomposites. UV-assisted Grigorieva, S.V. Dubonos, A.A. Firsov, Two-dimensional gas of massless Dirac
photocatalytic reduction of graphene oxide, ACS Nano. 2 (2008) 14871491. fermions in graphene, Nature 438 (2005) 197200.