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Very Imp Graphene Synthesis

Very Imp Graphene Synthesis

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21116
Phys. Chem. Chem. Phys.,
2011,
13
,21116–21120This journal is
c
the Owner Societies 2011
Citethis:
Phys. Chem. Chem. Phys 
.,2011,
13
,21116–21120
Competitive surface-enhanced Raman scattering effects in noble metalnanoparticle-decorated graphene sheets
Shengtong Sun and Peiyi Wu*
Received 8th August 2011, Accepted 26th September 2011
DOI: 10.1039/c1cp22727k
Herein, noble metal nanoparticle (Au or Ag NP) decorated graphene sheets, fabricated accordingto a facile one-pot environmentally friendly method, are used as good substrates for theinvestigation of the combined surface-enhanced Raman scattering (SERS) effect, where both theelectromagnetic mechanism and the chemical mechanism effects coexist among the Au or Ag NPs,graphene sheets and the absorbed analytes. Our results show that, in aqueous solution, the SERSeffect of both the Au and Ag NPs on the absorbed probe molecules and on graphene iscompetitive, which varies dependent on the species and the concentration of the absorbed probemolecule. By a detailed comparison of three probe molecules (rhodamine 6G, nile blue A, and4-aminobenzenethiol) with different coupling abilities to the graphene sheets, we finally attributethis phenomenon to the result of the strong suppressing effect of the macrocyclic probe moleculeson the SERS of graphene, induced by charge transfer, as the probe molecules are coupled to thegraphene sheets. This competitive effect is a non-ignorable phenomenon when graphene/Au or Agnanocomposites are used as SERS substrates, and our study may deepen our understanding of the SERS mechanism.
Introduction
Since its inception in the late 1970s, surface-enhanced Ramanscattering (SERS) has been proven to be a powerful andreliable analytical tool for the ultra-sensitive detection of analytes even at the single-molecule level.
1
Due to the signifi-cant increase in the cross-section of Raman scattering, SERScan enhance the Raman signal by a factor of 10
6
, and even asmuch as 10
14
, when an analyte is placed in the vicinity of thesurface of a plasmonic nanostructure.
2
The origins of theSERS effect is still in dispute, but may be attributed to twopossible sources: the electromagnetic mechanism (EM), whichis based on surface plasmon resonance (a factor of 10
6
 –10
8
enhancement)andthechemicalmechanism(CM),whichisbasedon charge transfer (usually a factor of 10–100 enhancement).
2
Traditionally, SERS substrates are based on the roughsurface of a noble metal taking advantage of the EM, mostlyAu and Ag, and involves depositing a thin film using electro-chemical or vacuum evaporation methods,
3
nanospherelithography,
4
or nanocrystal colloids,
5
etc.
Recently, graphenehas been shown to have a clear CM Raman enhancing effect,due to its unique flexible and smooth 2D honeycomb structurewith a one-atom thickness.
6
Several studies suggest thatgraphene is an excellent SERS substrate for absorbed speciesowing to it efficiently quenching the interfering excited-stateluminescence.
6,7
Ontheother hand, either placing grapheneona Ag film
8
or depositing arrays of Au or Ag nanoparticles(NPs) on graphene
9
induce a large enhancement in the Ramansignal of graphene. Additionally, combination of Au or Agand graphene sheets can also be used for the detection of lowconcentration molecules.
10
By decorating Au or Ag NPs ongraphene sheets, a coupled EM effect caused by the aggre-gation of the nanoparticles and strong electronic interactionsbetween Au or Ag NPs and the graphene sheets are consideredto be responsible for the significantly enhanced Raman signalof the analytes.
11
However, the acquisition of the enhancedRaman signal of the absorbed molecules on Au or Ag NP-decorated graphene sheets cannot always be as successful asnanocrystal colloids or graphene sheets alone.
11
b
It may bereasonable to suggest that the coexistence of the EM and theCM effects among the Au or Ag NPs, graphene sheets and theabsorbed analytes makes the case much more complicated.Herein, noble metal nanoparticle (Au or Ag NP) decoratedgraphene sheets were fabricated for use as good SERS sub-strates to distinguish the combined SERS effect when both theEM and the CM effects coexist among the Au or Ag NPs,graphene sheets and absorbed analytes. Our results show that,in aqueous solution, the SERS effect of both the Au and AgNPs on the absorbed probe molecules and on graphene, as wellas that of graphene on the probe molecules, are competitiveand vary dependent on the species and the concentration of the
The Key Laboratory of Molecular Engineering of Polymers,Ministry of Education, Department of Macromolecular Science,and the Laboratory of Advanced Materials, Fudan University,Shanghai 200433, China. E-mail: peiyiwu@fudan.edu.cn
PCCP
www.rsc.org/pccp
PAPER
   D  o  w  n   l  o  a   d  e   d   b  y   I  n   d   i  a  n   I  n  s   t   i   t  u   t  e  o   f   S  c   i  e  n  c  e  o  n   0   8   D  e  c  e  m   b  e  r   2   0   1   2   P  u   b   l   i  s   h  e   d  o  n   2   1   O  c   t  o   b  e  r   2   0   1   1  o  n   h   t   t  p  :   /   /  p  u   b  s .  r  s  c .  o  r  g   |   d  o   i  :   1   0 .   1   0   3   9   /   C   1   C   P   2   2   7   2   7   K
View Article Online / Journal Homepage / Table of Contents for this issue
 
 This journal is
c
the Owner Societies 2011
Phys. Chem. Chem. Phys.,
2011,
13
,21116–21120 21117
absorbed probe molecules. A proposed mechanism is alsopresented to account for this phenomenon.
Experimental
Preparation of graphene oxide (GO)
GO was prepared by a modified Hummers’ method.
12
Briefly,expandible graphite powders (5 g, 8000 mesh, Aladdin Co.Ltd.) and sodium nitrate (2.5 g) were mixed in concentratedH
2
SO
4
(115 mL) at 0
1
C, followed by the addition of potassiumpermanganate (15 g) under vigorous stirring. After increasingthe temperature to 35
1
C, excess deionized water (300 mL) wasadded to the mixture before stirring for 30 min and thetemperature was then increased to 90
1
C for 15 min beforeadding 30% H
2
O
2
(100 mL). The resulting suspension wasfiltered,washedwith5%HClanddialyzedfor7daystoremovethe remaining metal species. The GO aqueous dispersion wasdiluted prior to use.
Preparation of graphene/Au or Ag nanocomposites
Graphene/Au or Ag nanocomposites were prepared accordingto a modified method detailed in a previous report.
13
In brief,Au or Ag nanoparticle-decorated graphene sheets were prepared
via
a facile one-pot method. HAuCl
4
or AgNO
3
(5.0 mM),graphene oxide (0.1 mg mL
À
1
) and sodium citrate (10 mg mL
À
1
)were mixed with the assistance of sonication for 2 min and thenplacedinanoilbathat100
1
Cfor24hwithstirring.Afterwashingby centrifugation until the supernatant was colorless, theresulting graphene/Au or Ag nanocomposites were re-dispersedin water (graphene, 0.1 mg mL
À
1
) prior to use.
Characterization
The UV–vis spectra of graphene/Au and graphene/Ag disper-sions (graphene, 0.01 mg mL
À
1
) were measured on a HitachiU-2910 spectrophotometer. X-Ray diffraction (XRD) patternswere acquired by a D8 ADVANCE and DAVINCI.DESIGN(Bruker) X’pert diffractometer with Cu K
a
radiation. High-resolution transmission electron microscopy (HRTEM) imageswere taken with a JEOL JEM 2011 at 200 kV. The samples forRaman and SERS measurements were all prepared by placingthe aqueous solutions in capillary tubes and the spectra recordedon a Renishaw inVia Reflex micro-Raman spectrometer withHe/Nelaserexcitationat632.8nm.A200
Â
objectivewasusedtofocus the laser beam and to collect the Raman signals. To ensurethe obtained spectra were comparable, the settings, including thelasers’ power and the exposure time, were all the same.
Results and discussion
Au and Ag NP-decorated graphene sheets (referred to asgraphene/Au and graphene/Ag) were prepared
via
a facileone-pot environmentally friendly method by heating a mixedaqueous solution of HAuCl
4
(AgNO
3
), graphene oxide andsodium citrate at 100
1
C for 24 h. After washing several timesto remove the residual salts, the resulting graphene/Au andgraphene/Ag nanocomposites were well dispersed in water, asshown in Fig. 1a. From the UV–vis spectra, we can observethe characteristic absorption peak at 260 nm for the restored
p
 – 
p
conjugated structure of the graphene sheets
14
due to thereduction of graphene oxide (229 nm)
via
sodium citrate.Additionally, there is also another characteristic surface plasmonabsorption peak for the Au NPs (539 nm) and for the Ag NPs(405 nm),
15
which implies the formation of graphene/Au andgraphene/Ag nanocomposites. The XRD patterns of graphene/Au and graphene/Ag (Fig. 1b) both exhibit four obvious peakscorresponding to the (111), (200), (220) and (311) diffractions,indicating that the Au and Ag NPs both exist in the crystallinestate. TEM and HRTEM images shows that the Au NPs(10–30nm)andAgNPs(10–35nm)arehomogeneouslyattachedto the graphene sheets, which can be used as agood substrate forinvestigating the combining SERS effect. Due to the completereduction of graphene oxide and Au or Ag NPs by sodiumcitrate, the mass ratio of graphene:Au and graphene:Ag in theresulting nanocomposites can be estimated to be 1:10 and 1:5,respectively.In our study, the laser excitation wavelength was alwaysfixed at 632.8 nm as Auand Ag NPs have a rather large Ramansignal enhancement relative to graphene at an excitation of 632.8 nm, compared to other excitation wavelengths.
9
b
,
c
Basedon this laser excitation, three commonly used Raman probemolecules were chosen for comparison (Fig. 3). Rhodamine 6G(R6G) is a cationic dye possessing a maximum absorption bandinthevisibledomainaround 530nm (non-resonant excitation);
16
nile blue A (NBA) is also a cationic dye with a maximumabsorption band around 625 nm (resonant excitation), but witha larger macrocyclic conjugated structure than R6G to form
Fig. 1
(a) UV–vis spectra of graphene/Au and graphene/Ag nano-composites, reduced by sodium citrate, in their aqueous dispersions.The inset is the photograph of the aqueous dispersions (graphene,0.01 mg mL
À
1
) (left: graphene/Au; right: graphene/Ag). (b) XRDpatterns of graphene/Au and graphene/Ag nanocomposites. (c) TEMimages of graphene/Au (left) and graphene/Ag (right) nanocomposites.The insets are the corresponding HRTEM images. (d) Size distributionhistograms of the graphene/Au and graphene/Ag nanocomposites.
   D  o  w  n   l  o  a   d  e   d   b  y   I  n   d   i  a  n   I  n  s   t   i   t  u   t  e  o   f   S  c   i  e  n  c  e  o  n   0   8   D  e  c  e  m   b  e  r   2   0   1   2   P  u   b   l   i  s   h  e   d  o  n   2   1   O  c   t  o   b  e  r   2   0   1   1  o  n   h   t   t  p  :   /   /  p  u   b  s .  r  s  c .  o  r  g   |   d  o   i  :   1   0 .   1   0   3   9   /   C   1   C   P   2   2   7   2   7   K
View Article Online
 
21118
Phys. Chem. Chem. Phys.,
2011,
13
,21116–21120This journal is
c
the Owner Societies 2011
p
 – 
p
stacking, which couples to the graphene sheets;
17
4-amino-benzenethiol (4-ABT) is well-known to preferentially bind Auand Ag NPs
via
Au–S and Ag–S bonds and has the weakestconjugated structure among the probe molecules invesitgated.
18
WefirstexaminedtheSERSeffectofgraphenebydecoratingitwithAuandAgNPs,asshowninFig.2.Anapparentenhancingeffect of the Raman signals of graphene can be observed afterthe decoration with the noble metal nanoparticles, which is inaccordance with previous reports.
9
The enhancement factorcan be estimated to be about 3.6 for graphene/Au and 13.1 forgraphene/Ag, according to the G peak, which mainly arisesfrom the EM effect based on the charge transfer betweengraphene and the Au or Ag NPs.
9
b
Ag is known to have alarger SERS effect than Au. It is also notable that, after thedecoration with the different nanoparticles, the D and Gpeaks shift in opposite directions as compared to those of graphene without any decoration. This can be attributed to thedifferent types of doping induced by decoration of graphenewith either Au or Ag NPs (Au, p-type doping; Ag, n-typedoping).
9
AstheRamanprobemoleculeswereaddedtoeithergraphene/Au or graphene/Ag aqueous dispersions, it is interesting to notethat acompetitiveSERSeffect canalways beobserved, as shownin Fig. 3. For all the three probe molecules, when the concen-trationisrelativelyhigh(1
Â
10
À
4
M),aSERSeffectoftheAuorAg NPs on the probe molecules can be identified, while the effecton graphene is suppressed. However, when the concentrationdecreases below 1
Â
10
À
5
M, only the SERS spectra of graphenecan be detected. It seems strange because, for either the CM of graphene or the EM of the Au or Ag NP colloids individually,the intensities of the enhanced Raman signals of the probemolecules should gradually decrease as the concentrationdecreases as has been commonly observed.
5,6
Thus, we presumed
Fig. 2
Raman spectra of graphene, graphene/Au and graphene/Agnanocomposites in their aqueous dispersions (graphene, 0.1 mg mL
À
1
).
Fig. 3
Raman spectra of R6G, NBA and 4-ABT in graphene/Au (top) and graphene/Ag (bottom) aqueous dispersions (graphene, 0.1 mg mL
À
1
) withdifferentconcentrationsvaryingfrom1
Â
10
À
4
to1
Â
10
À
6
M.Forcomparison,the Ramanspectraof thepurecomponents(R6G,1
Â
10
À
2
Maqueoussolution; NBA and 4-ABT, as solids) as well as those of the graphene/Au and graphene/Ag nanocomposites without any analytes are also presented.
   D  o  w  n   l  o  a   d  e   d   b  y   I  n   d   i  a  n   I  n  s   t   i   t  u   t  e  o   f   S  c   i  e  n  c  e  o  n   0   8   D  e  c  e  m   b  e  r   2   0   1   2   P  u   b   l   i  s   h  e   d  o  n   2   1   O  c   t  o   b  e  r   2   0   1   1  o  n   h   t   t  p  :   /   /  p  u   b  s .  r  s  c .  o  r  g   |   d  o   i  :   1   0 .   1   0   3   9   /   C   1   C   P   2   2   7   2   7   K
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