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absorbed probe molecules. A proposed mechanism is alsopresented to account for this phenomenon.
Preparation of graphene oxide (GO)
GO was prepared by a modiﬁed Hummers’ method.
Brieﬂy,expandible graphite powders (5 g, 8000 mesh, Aladdin Co.Ltd.) and sodium nitrate (2.5 g) were mixed in concentratedH
(115 mL) at 0
C, followed by the addition of potassiumpermanganate (15 g) under vigorous stirring. After increasingthe temperature to 35
C, excess deionized water (300 mL) wasadded to the mixture before stirring for 30 min and thetemperature was then increased to 90
C for 15 min beforeadding 30% H
(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.
In brief,Au or Ag nanoparticle-decorated graphene sheets were prepared
a facile one-pot method. HAuCl
(5.0 mM),graphene oxide (0.1 mg mL
) and sodium citrate (10 mg mL
)were mixed with the assistance of sonication for 2 min and thenplacedinanoilbathat100
Cfor24hwithstirring.Afterwashingby centrifugation until the supernatant was colorless, theresulting graphene/Au or Ag nanocomposites were re-dispersedin water (graphene, 0.1 mg mL
) prior to use.
The UV–vis spectra of graphene/Au and graphene/Ag disper-sions (graphene, 0.01 mg mL
) 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
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
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
a facileone-pot environmentally friendly method by heating a mixedaqueous solution of HAuCl
), graphene oxide andsodium citrate at 100
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
conjugated structure of the graphene sheets
due to thereduction of graphene oxide (229 nm)
sodium citrate.Additionally, there is also another characteristic surface plasmonabsorption peak for the Au NPs (539 nm) and for the Ag NPs(405 nm),
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.
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);
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
(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
) (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.
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