Sensors and Actuators B 231 (2016) 609–614

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Ag-Au alloy nanoparticles: Synthesis and in situ monitoring SERS of

plasmonic catalysis
Qingyan Han, Chengyun Zhang, Wei Gao, Zhihang Han, Tingzhuo Liu, Caixia Li,
Zhaojin Wang, Enjie He, Hairong Zheng ∗
School of Physics and Information Technology, Shaanxi Normal University, 710119 Xi’an, China

a r t i c l e i n f o a b s t r a c t

Article history: Noble metal nanostructures are currently of great interest for their unique plasmonic property and poten-
Received 23 October 2015 tial applications in catalysis and surface-enhanced spectroscopy. However, the application of plasmonic
Received in revised form 16 March 2016 nanostructures for quantitatively in situ SERS monitoring of the catalytic reaction has been a great chal-
Accepted 16 March 2016
lenge for investigators because combining plasmonics with catalysis requires the same kind of noble
Available online 17 March 2016
metal nanoparticles (NPs) in two very different size regimes. Herein, We have demonstrated a facile wet
chemical method to synthesize Au-Ag alloy plasmonic NPs that could combine the desired plasmonic
Keywords:
and catalytic properties with same NPs. The catalytic activity of Au-Ag alloy NPs using the reduction of
Au-Ag alloy nanoparticles
Surface plasmon resonance
4-nitrothiophenol (4-NTP) by sodium borohydride (NaBH4 ) is chosen as a model reaction. The signals
Surface-enhanced Raman scattering of the reaction processes are detected and identified through in situ SERS spectroscopy with high sensi-
Plasmonic catalysis tivity. The insights gained by current study may serve as a promising and powerful technique for better
investigation in the heterogeneous catalysis. Moreover, the reduction of aromatic nitro compounds with
prepared Au-Ag alloy NPs also provides potential application in sewage treatment.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction in catalysis could improve the feasibility of wastewater treatment

technique.
Plasmonic metal nanocrystals exhibit unique properties with To investigate metal-catalyzed reactions, several kinds of
potential application in many fields, which include catalysis [1], technique have been successfully employed for conducting the nec-
photovoltaics [2], sensing [3], and photothermal therapy [4]. The essary measurement, which include UV–vis-infrared absorption
plasmonic responses strongly depend on the type, size, config- [14,15], Raman or surface-enhanced Raman scattering (SERS) spec-
uration and the surrounding environment of the noble metal troscopy [16,18]. However, the absorption in UV–vis regime can
nanocrystals [5–7]. Recently, through integrating two or more only offer very limited chemical information and the application of
metal materials into a single entity, the plasmonic property can infrared spectroscopy to aqueous system is not a good choice due
be significantly extended due to synergistic effect [1,8]. For exam- to strong water absorption of the system. Compared with optical
ple, hybrid, core-shell or alloy structures can produce superior absorption, Raman scattering, especially SERS has obvious advan-
and sometimes unprecedented physical and chemical properties tages for in situ monitoring the interfacial reaction. SERS mainly
in catalysis and optics for both fundamental investigations and utilizes the enhanced electromagnetic field and localized surface
technological applications [9,10]. Various metal nanocrystals have plasmon resonance (LSPR) to get enhanced Raman scattering signal
been prepared using wet chemistry methods [6,11], which pro- from target molecules, which is generated at some metal surfaces
duce plasmonic resonances in the visible to near-infrared regions, upon laser excitation [19,20]. Additionally, the technique of SERS
facile surface conjugation to a variety of chemical and biomolec- spectroscopy can provide non-destructive and ultra-sensitive char-
ular ligands [12], biocompatibility and catalytic effect towards acterization down to a single-molecule regime [21]. Thus, as a
many important oxidization reactions [8,13]. These applications powerful analysis and characterization technique, SERS-based sig-
nal detection and molecular identification combine the advantages
of high chemical specificity (vibrational Raman scattering), high
sensitivity (electromagnetic and chemical enhancement), and sur-
∗ Corresponding author.
face selectivity (near-field enhancement) [22–24]. Unfortunately,
E-mail address: [email protected] (H. Zheng).

http://dx.doi.org/10.1016/j.snb.2016.03.068
0925-4005/© 2016 Elsevier B.V. All rights reserved.
610 Q. Han et al. / Sensors and Actuators B 231 (2016) 609–614

the combination of desired plasmonic and superior catalytic prop- 2.4. Characterization
erties on the same kind of noble metal nanocrystals has been a
challenge because they typically require metal nanoparticles (NPs) The prepared nanostructures were characterized in several
in two drastically different size regimes [25]. For example, small ways, Transmission electron microscope (TEM) images were
Au NPs have shown good catalytic activity, they are active even obtained with JEOL 2100 TEM at an acceleration voltage of 200 kV.
in at room temperature [26,27], but the efficient Raman or SERS Scanning TEM (STEM) images were collected on a FEI-Tecnai G2 F20
signals are difficult to be detected because of their very small Field-emission transmission electron microscope (FE-TEM) operat-
scattering cross sections. On the other hand, larger Au NPs show ing at 200 kV accelerating voltage. UV–vis-NIR absorption spectra
geometry-dependent optical properties that can provide necessary were measured by using a Perkin Elmer Lambda 950 spectrome-
SERS enhancement [17], but their catalytic activity decay rapidly. ter. Raman spectral measurements were conducted with a LabRam
Ag NPs have much stronger surface plasmon resonance than Au due HR Evolution Raman system (Jobin-Yvon). The wavelength of the
to its proper electronic structure and dielectric function [12], but excitation light was 633 nm. The numerical calculation on the elec-
they have not been fully used in practical applications due to their tromagnetic field distribution was carried out with the application
poor chemical stability and aggregation effect [28]. Therefore, it is of 3D finite element method [29].
very important to combine superior catalytic and high plasmonic
activity simultaneously in one nanostructure.
In current paper, a strategy to facilely synthesize Au-Ag alloy 3. Results and discussion
NPs with good dispersibility in aqueous solution is presented. By
adjusting the ratio of two metals, we obtain a tunable localized sur- 3.1. Synthetic mechanism and plasmonic properties
face plasmon resonance (LSPR) with high intensity in visible region.
The Au-Ag alloy NPs show excellent SERS characteristics and high As presented in the experimental section, Au-Ag alloy NPs were
catalytic activity. Their potential application for in situ SERS mon- prepared by using wet chemistry method. Fig. 1(a) shows the TEM
itoring of the quantitative reaction of 4- nitrothiophenol (4-NTP) image of Au-Ag alloy NPs as synthesized, which indicates the uni-
reduction to 4-aminothiophenol (4-ATP) by NaBH4 in colloidal is formity of the products. The average size of Au-Ag alloy Nps are
presented too. around 33 ± 2 nm. To confirm the distribution of each element in
the as-prepared Au-Ag alloy NPs, FE-TEM analysis were conducted.
Fig. 1(b)–(e) are STEM images of typical Au-Ag alloy NPs, which
2. Experimental were used as elemental mapping analysis in later discussion. Line-
scanning profiling analysis shows that both Au and Ag distributed
2.1. Materials homogeneously across the particles (Fig. 1(b)). STEM-energy dis-
persive X-ray (STEM-EDX) elemental mapping of Au and Ag were
Sodium citrate (C6 H5 Na3 O7 , 99%), silver nitrate (AgNO3 , 99.8%), separately shown in Fig. 1(c) and (d), which further conformed the
hydrogen tetrachloroauric acid (HAuCl4 ·4H2 O, 99%), sodium boro- composition of Au-Ag alloy NPs. The full coverage of both Au and
hydride (NaBH4 , 98%) and ethanol were supplied by Sinopharm Ag indicates the alloy structure of the sample. The merged image
Chemical Reagent Co., Ltd. (China). 4-nitrothiophenol (4-NTP, 80%) (Fig. 1(e)) further supports the complete overlapping of two metal
was purchased from Sigma-Aldrich. All chemical reagents were components.
used as received without further purification. Deionized (DI) water To characterize the property of NPs, surface plasmon reso-
was used throughout experiments. nance (SPR) was investigated by UV–vis and NIR absorption spectra.
Fig. 1(f) presented normalized extinction spectra of as-prepared Au,
Ag, and Au-Ag alloy NPs. Au and Ag NPs exhibit characteristic SPR
peaks at about 523 nm and 422 nm [30,31]. As the ratio content
2.2. Synthesis of Au-Ag alloy nanoparticles
of Au to Ag increases in alloy Au-Ag NPs, spectral red-shift occurs
for the SPR from the side of Ag NPs towards that of the Au NPs.
Au-Ag alloy NPs were synthesized via reduction of AgNO3
The SPR peak at ␭SPR = 472 nm for Au-Ag presented in the figure
and HAuCl4 ·4H2 O with citrate. For Au-Ag alloy NPs, HAuCl4 ·4H2 O
matches well with the composition alloy NPs. The corresponding
(0.01 M, 1 ml) and AgNO3 (0.01 M, 1 ml) were dissolved in 78 ml of
photographs shown in the inset of Fig. 1(f) demonstrate a gradual
boiled deionized water firstly while stirring. Then, 8 ml of sodium
color change from yellow to wine red with the content increase
citrate (0.1 M) was quickly added into the solution. In this case, the
of Au. All of these results confirm the formation of monodispersed
mixture was kept at 100 ◦ C for 15 min with continuous stirring. The
Au-Ag alloy NPs in current study.
reaction was completed by cooling it down to room temperature.
To better understand the plasmonic property of metal NPs, the
The synthesized NPs were washed and centrifuged for several times
distribution of local electric field as shown in Fig. 2 was calculated
before they were dispersed in water and kept in the dark at room
by finite element method (COMSOL Multiphysics) [29]. The basic
temperature.
data on the shape and size of Au, Ag and Au-Ag alloy NPs were
from the experimental measurements. Fig. 2 shows the calculated
extinction spectra for an individual particle at a normally incident
2.3. In situ monitoring of the catalytic reaction with SERS light excitation. The extinction peaks for Ag, Au-Ag alloy and Au
NPs locate at 396, 470, and 522 nm, respectively. Ag NPs exhibit a
10 ␮l of 10−3 M 4-NTP ethanol solution was added to 1 ml narrower spectral width and higher resonance intensity. The sim-
colloidal suspension of Au-Ag alloy NPs and incubated at room ulated electromagnetic field distributions of the Ag, Au-Ag alloy,
temperature overnight, which formed a 4-NTP molecular self- and Au NPs under the resonance excitations are presented in the
assembled monolayer (SAM) on the surface of NPs. Then the Au-Ag right panel of Fig. 2. It can be seen that Au-Ag alloy NPs exhibit a
alloy NPs were washed for 2 times with water and resuspended stronger electric field than Au NPs. Comparing with the numerical
in 400 ␮l water. 100 ␮l of NPs-catalyzed 4-NTP reduction occurred simulation, we notice that a red-shift occurred in the LSPR spec-
upon the addition of 200 ␮l of 10−2 M NaBH4 into a 0.4 ml quartz tra obtained by the experimental observation, and the biggest shift
vessel at room temperature. The kinetics of the catalyzed reactions presented for Ag particles. For the observed LSPR spectral shift, the
was measured in situ with real-time monitoring SERS. possible assembly effect existed in the experimental measurement
 Q. Han et al. / Sensors and Actuators B 231 (2016) 609–614 611

Fig. 1. Characterization of metal NPs. (a) TEM image of Au-Ag alloy NPs. (b) STEM image and cross-sectional compositional line profiles of Au-Ag alloy NPs. (c) and (d)
STEM-EDX elemental mapping image of Au(d) and Ag(e) from a single Au-Ag alloy nanoparticle. (e) The merged image of (c) and (d). (f) Absorption spectra of Ag, Au-Ag
alloy and Au NPs, which correspond to green, blue and red curves. Insets are photographs of the corresponding samples. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)

Incident wavelength dependence of the electromagnetic field

amplification is one important characters of LSPR and affects the
plasmonic effect significantly. The numerical simulation the elec-
tromagnetic field distributions of the Ag, Au-Ag alloy, and Au
nanoparticle are carried out with the excitation wavelength of
532 nm, 633 nm, and 785 nm (Fig. S1). The highest intensity of the
electromagnetic field was obtained at the excitation of 532 nm,
while the lowest one was with 785 nm. The intensity of the elec-
tromagnetic field obtained with 633 nm excitation was in between.
However, when the system is excited by 532 nm laser, the inten-
sities of Raman scattering bands for 4-NTP, 4-ATP, and DMAB are
much weaker than that with the other wavelength excitation. It is
reported that the intensity of the band at about 1081 cm−1 mostly
depends on the enhancement caused by LSPR, and the intensity
of the band at 1081 cm−1 for 4-ATP and DMAB decreases follow-
Fig. 2. Left panel: extinction spectra of Ag, Au-Ag alloy and Au nanoparticle in water ing the order of excitation wavelength of 633 nm > 785 nm > 532 nm
solution, the diameter of the particle is 33 nm. Right panel: spatial electric field [34]. Therefore, we took 633 nm laser as an excitation light in the
distributions for Ag, Au-Ag alloy and Au nanoparticle. The color bars at the bot-
following study.
tom represent the amplitude of |E/E0 |, where E is the local electric field around the
nanoparticle, and E0 is the incident electric field. (For interpretation of the refer-
ences to colour in this figure legend, the reader is referred to the web version of this 3.2. In situ monitoring of catalytic reaction with SERS
article.)
Since the simultaneous introduction of Ag and Au are fulfilled,
it is very important to investigate the in situ real-time monitoring
should be the reason of it. Since only single nanoparticle is to be SERS of catalytic reaction with presented Au-Ag alloy NPs. Owing
considered in the calculation, therefore the corresponding experi- to the synergistic effect of the metal components, the plasmonic
mental result for the comparison should be exactly from very well activity of Ag increases while catalytically active Au is presented at
isolated single particles. According to the experimental investiga- the same time. In contrast, no catalytic activity is observed without
tion, the practical metal particle system usually contains more or the introduction of Ag. To demonstrate the catalytic and SERS activ-
less nanoparticle clusters during the measurement even though the ity of Au-Ag alloy NPs, a proper material for this proof-of-concept
characterization results present very good dispersibility. For the study and practical applications are required. Here, we investigate
systems of Au, Ag and Au-Ag alloy NPs, Ag NPs have much lower the reduction of aromatic nitro compounds (R-NO2 ) to the aniline
chemical stability and are easier to be aggregated. The aggregation derivative (R-NH2 ) at room temperature (Fig. 3), which would be
effect would lead to an increase of the particle size and charge sep- useful for environment governance and the synthesis of fine chem-
aration, leading to a lower frequency for the collective oscillation of ical.
free electrons and thus a red-shift of the LSPR in the experimental The time-resolved SERS monitoring can gain quanti-
observation comparing with the numerical simulation [32,33]. tative insights into the kinetics and mechanism study of
612 Q. Han et al. / Sensors and Actuators B 231 (2016) 609–614

Fig. 3. A tentative mechanism of the chemical reduction of surface-adsorbed 4-NTP by NaBH4 to DMAB and finally to 4-ATP catalyzed by Au-Ag alloy NPs.

symmetric stretching, N N stretching, and C H in-plane bending

modes of 4, 4 -dimercapto-azobenzene (4, 4 -DMAB), respectively
[37]. With increasing of reaction time (from bottom to top in Fig. 4),
the intensity of SERS signal from 4, 4 -DMAB initially increases
and then decreases ultimately, indicating that NO2 groups start
to be reduced. The band arising from C H wagging and phenyl
ring modes of 4-NTP at 854 and 1571 cm−1 also decreases grad-
ually, concomitant with the intensity of a new band at 1595 cm
−1 increases and an additional characteristic signal of 4-ATP at

1489 cm−1 appears (Fig. 4 top) [35]. Therefore, one can conclude
that the final reaction product is 4-ATP for the reduction of 4-NTP
by NaBH4 , which demonstrates the catalytic activity of Au-Ag alloy
NPs for in situ chemical process monitoring.
However, different results were observed from reaction system
that contained Au or Ag NPs. For SAM of 4-NTP on Au NPs, the SERS
spectrum with no obvious change was observed under the simi-
lar conditions with the catalytic reaction of Au-Ag alloy NPs (Fig.
Fig. 4. SERS spectra recorded during the Au-Ag alloy NPs reduction of an aromatic S3), demonstrating that Au NPs have a very low catalytic activity
nitro compound after addition of NaBH4 solution for different reaction time. in this case [37]. While for a SAM of 4-NTP on Ag NPs experiment,
vibrational Raman bands from 4,4 -dimercapto-azobenzene (4,4 -
DMAB) were detected, which are at 1144, 1390, and 1436 cm−1
due to C N symmetric stretching, N N stretching, and C H in-
nanoparticle-catalyzed reaction. Au-Ag alloy nanoparticle-
plane bending modes (Fig. S4). Interestingly, these three bands are
catalyzed reaction through the reduction of 4-NTP by NaBH4 was
assigned to 4-NTP instead of 4-ATP in SERS spectrum [12,25]. Obvi-
chosen as a model reaction, which will be compared to the catalytic
ously, the catalytic activity of Au-Ag alloy NPs is better than the
activity of Ag and Au. Both the intrinsic reaction mechanism and
conventional monometallic Au or Ag NPs. This may be caused by
kinetics can be studied in real time by online detecting SERS
the dramatic increase of the catalytic activity when alloying of silver
signals from themonolayer molecule preadsorbed on the surface
with gold.
of metal NPs. Thus, the identification of transient intermediates
It is well-known that Au NPs less than 5 nm in diameter have
during the reaction processes became possible. To obtain the
remarkable catalytic activity, but the plasmon resonance is weak
samples for conducting SERS measurement, colloidal suspension
due to small scattering cross section [38]. However, Au-Ag NPs
of NPs was incubated with ethanolic solution of 4-NTP at room
with a size of 33 nm shows high catalytic activity by using SERS
temperature overnight, which formed a 4-NTP molecular SAM at
as an ultrasensitive spectroscopic technique to precisely monitor
the surface of NPs. The SAM of 4-NTP on the surface of metal NPs
the process in present work. This observation suggests that the
underwent a two-step reduction process upon the introduction
size and structure of Au-Ag alloy NPs seem not are a very criti-
of NaBH4 at room temperature, for which the final product is
cal factors for the reaction system. Although we are still on the way
4-ATP. As shown in Fig. 4, the SERS spectrum of 4-NTP monolayer
to understand the underlying mechanism of the catalysis by this
exhibite four characteristic vibrational bands at 854, 1081, 1338,
alloy NPs, we believe that the presence of Ag plays a very impor-
and 1571 cm−1 , which correspond to C H wagging, C S stretching,
tant role in Au-Ag alloy NPs-catalyzed reaction. Au-Ag alloy NPs
O N O stretching, and the phenyl ring modes, respectively [35].
have presented a strongly synergistic effect in plasmonic and cat-
However, the feature of SERS signal for 4-NTP remains unchanged
alytic activity, which could bring us a new metal nanosystem with
at the beginning of ∼2 min in the presence of NaBH4 (Fig. S2). This
good catalytic property.
is most likely due to the formation of active surface hydrogen
species upon the adsorption of borohydride ions onto the surface
of Au-Ag NPs [36]. Therefore, the hydrogenation of 4-NTP was 4. Conclusion
initiated only when the concentration of surface hydrogen species
reached to the threshold. As the reaction proceeded, strong Raman In summary, a simple facile synthetic protocol was established
signal at 1338 cm−1 decreased gradually, and new vibrational for preparation the monodispersed Au-Ag alloy NPs, which inte-
Raman signals of the intermediate at 1144, 1390, and 1436 cm−1 grate both good plasmonic property of Ag and outstanding stability
appeared along the reaction pathway, which were due to C N of Au into a single bifunctional entity. In addition, the Au-Ag alloy
 Q. Han et al. / Sensors and Actuators B 231 (2016) 609–614 613

NPs exhibit very well catalytic activity and strong SERS effect, which [18] H. Huang, H. Li, J.J. Feng, A.J. Wang, One-step green synthesis of fluorescent
may be due to synergistic effect. The catalytic activity of Au-Ag bimetallic Au/Ag nanoclusters for temperature sensing and in vitro detection
of Fe3 +, Sens. Actuators B 223 (2016) 550–556.
alloy NPs and the mechanism of Au-Ag alloy NPs-catalyzed reac- [19] L.L. Kang, P. Xu, B. Zhang, H.H. Tsai, X.J. Han, H.L. Wang, Laser wavelength- and
tions are investigated with 4-NTP molecules by in situ real-time power-dependent plasmon-driven chemical reactions monitored using single
quantitative SERS, which ensure the signal detection on the inter- particle surface enhanced Raman spectroscopy, Chem. Commun. 49 (2013)
3389–3478.
mediate and final products. The study offers a new strategy that [20] G. Sinha, L.E. Depero, I. Alessandri, Recyclable SERS substrates based on
could be applied for the preparation of other alloy catalysts for Au-coated ZnO nanorods, ACS Appl. Mater. Interfaces 3 (2011) 2557–2563.
diverse uses by synergy effects. Moreover, with the development of [21] J.F. Li, Y.F. Huang, Y. Ding, Z.L. Yang, S.B. Li, X.S. Zhou, F.R. Fan, W. Zhang, Z.Y.
Zhou, D.Y. Wu, B. Ren, Z.L. Wang, Z.Q. Tian, Shell-isolated
SERS-based synergy technique and catalytic products, we believed
nanoparticle-enhanced Raman spectroscopy, Nature 464 (2010) 392–395.
that the unprecedented improvement in catalytic reaction of aro- [22] Y. Wei, C. Cao, R.C. Jin, C.A. Mirkin, Nanoparticles with Raman spectroscopic
matic nitro compound is on the way to achieve, which very possibly fingerprints for DNA and RNA detection, Science 297 (2002) 1536–1540.
[23] S.M. Nie, S.R. Emory, Probing single molecules and single nanoparticles by
opens a new window for environmental protection.
surface-enhanced Raman scattering, Science 275 (1997) 1102–1106.
[24] K.N. Heck, B.G. Janesko, G.E. Scuseria, N.J. Halas, M.S. Wong, Observing
metal-catalyzed chemical reactions in situ using surface-enhanced Raman
Acknowledgments
spectroscopy on Pd-Au nanoshells, J. Am. Chem. Soc. 130 (2008)
16592–16600.
The work is supported by the National Science Foundation of [25] H. Jing, Q.F. Zhang, N. Large, C.M. Yu, D.A. Blom, P. Nordlander, H. Wang,
China (Grant 11174190, 11574190), the Fundamental Research Tunable plasmonic nanoparticles with catalytically active high-index facets,
Nano Lett. 14 (2014) 3674–3682.
Funds for Central Universities (Grants GK201504005), and Inno- [26] M.C. Daniel, D. Astruc, Gold nanoparticles: assembly, supramolecular
vation Funds of Graduate Programs SNNU (Grants 2015CXB011). chemistry, quantum-size-related properties, and applications toward biology,
catalysis, and nanotechnology, Chem. Rev. 104 (2004) 293–346.
[27] A.S.K. Hashmi, G.J. Hutchings, Gold catalysis, Angew. Chem. Int. Ed. 45 (2006)
Appendix A. Supplementary data 7896–7936.
[28] C.B. Gao, Y.X. Hu, M.S. Wang, M.F. Chi, Y.D. Yin, Fully alloyed Ag/Au
nanospheres: combining the plasmonic property of Ag with the stability of
Supplementary data associated with this article can be found, in Au, J. Am. Chem. Soc. 136 (2014) 7474–7479.
the online version, at http://dx.doi.org/10.1016/j.snb.2016.03.068. [29] P.B. Johnson, R.W. Christy, Optical constants of the noble metals, Phys. Rev. B
6 (1972) 4370–4379.
[30] D. Kim, J. Resasco, Y. Yu, A.M. Asiri, P.D. Yang, Synergistic geometric and
References electronic effects for electrochemical reduction of carbon dioxide using
gold-copper bimetallic nanoparticles, Nat. Commun. 52 (2014) 4948–4956.
[1] P. Christopher, H.L. Xin, S. Linic, Visible-light-enhanced catalytic oxidation [31] A. Panáček, L. Kvítek, R. Prucek, M. Kolář, R. Večeřová, N. Pizúrová, V.K.
reactions on plasmonic silver nanostructures, Nat. Chem. 3 (2011) 467–472. Sharma, T. Nevěčná, R. Zbořil, Silver colloid nanoparticles: synthesis,
[2] P.I. Geshev, U.C. Fischer, H. Fuchs, Calculation of tip enhanced Raman characterization, and their antibacterial activity, J. Phys. Chem. B. 110 (2006)
scattering caused by nanoparticle plasmons acting on a molecule placed near 16248–16253.
a metallic film, Phys. Rev. B 81 (2010) 125441. [32] M. Rycenga, C.M. Cobley, J. Zeng, W.Y. Li, C.H. Moran, Q. Zhang, D. Qin, Y.N.
[3] J. Homola, S.S. Yee, G. Gauglitz, Surface plasmon resonance sensors: review, Xia, Controlling the synthesis and assembly of silver nanostructures for
Sens. Actuators B 54 (1999) 3–15. plasmonic applications, Chem. Rev. 111 (2011) 3669–3712.
[4] J.W. Kim, E. Galanzha, E.V. Shashkov, H.M. Moon, V.P. Zharov, Golden carbon [33] N.G. Bastuı́s, F. Merkoçi, J. Piella, V. Puntes, Synthesis of highly monodisperse
nanotubes as multimodal photoacoustic and photothermal high-contrast citrate-stabilized silver nanoparticles of up to 200 nm: kinetic control and
molecular agents, Nat. Nanotechnol. 4 (2009) 688–694. catalytic properties, Chem. Mater. 26 (2014) 2836–2846.
[5] J. Dong, S.X. Qu, H.R. Zheng, Z.L. Zhang, J.N. Li, Y.P. Huo, G.A. Li, Simultaneous [34] Y.F. Huang, M. Zhang, L.B. Zhao, J.M. Feng, D.Y. Wu, B. Ren, Z.Q. Tian,
SEF and SERRS from silver fractal-like nanostructure, Sens. Actuators B 191 Activation of oxygen on gold and silver nanoparticles assisted by surface
(2014) 595–599. plasmon resonances, Angew. Chem. Int. Ed. 53 (2014) 2353–2357.
[6] I. Vassalini, E. Rotunno, L. Lazzarini, I. Alessandri, Stainless gold nanorods: [35] J.F. Huang, Y.H. Zhu, M. Lin, Q.X. Wang, L. Zhao, Y. Yang, K.X. Yao, Y. Han,
preserving shape, optical properties, and SERS activity in oxidative Site-specific growth of au-Pd alloy horns on Au nanorods: a platform for
environment, ACS Appl. Mater. Interfaces 7 (2015) 18794–18802. highly sensitive monitoring of catalytic reactions by surface enhancement
[7] J.N. Li, T.Z. Liu, H.R. Zheng, F. Gao, J. Dong, Z.L. Zhang, Z.Y. Zhang, Plasmon Raman spectroscopy, J. Am. Chem. Soc. 135 (2013) 8552–8561.
resonances and strong electric field enhancements in side-by-side tangent [36] P. Hervés, M. Pérez-Lorenzo, L.M. Liz-Marzán, J. Dzubiella, Y. Lu, M. Ballauff,
nanospheroid homodimers, Opt. Express 21 (2013) 17176–17185. Catalysis by metallic nanoparticles in aqueous solution: model reactions,
[8] X.C. Ye, J. Chen, B.T. Diroll, C.B. Murray, Tunable plasmonic coupling in Chem. Soc. Rev. 41 (2012) 5577–5587.
self-assembled binary nanocrystal superlattices studied by correlated optical [37] W. Xie, B. Walkenfort, S. Schlücker, Label-free SERS monitoring of chemical
microspectrophotometry and electron microscopy, Nano Lett. 13 (2013) reactions catalyzed by small gold nanoparticles using 3D plasmonic
1291–1297. superstructures, J. Am. Chem. Soc. 135 (2013) 1657–1660.
[9] J. Dong, Z.L. Zhang, H.R. Zheng, M.T. Sun, Recent progress on [38] J.A. Scholl, A.L. Koh, J.A. Dionne, Quantum plasmon resonances of individual
plasmon-enhanced fluorescence, Nanophotonics 4 (2015) 472–490. metallic nanoparticles, Nature 483 (2012) 421–427.
[10] C. Ayala-Orozco, J.G. Liu, M.W. Knight, Y.M. Wang, J. Day, P. Nordlander, N.J.
Halas, Fluorescence enhancement of molecules inside a gold
nanomatryoshka, Nano Lett. 14 (2014) 2926–2933. Biographies
[11] C.M. Cobley, S.E. Skrabalak, D.J. Campbell, Y.N. Xia, Shape-controlled synthesis
of silver nanoparticles for plasmonic and sensing applications, Plasmonics 9
(2009) 171–179.
Qingyan Han received her B.S. degree in physics from Baotou Teachers College in
[12] E. Katz, I. Willner, Integrated nanoparticle-biomolecule hybrid systems:
2011. Afterwards, she moved to Shaanxi Normal University as a master student
synthesis, properties, and applications, Angew. Chem. Int. Ed. 43 (2004)
under the supervision of Professor Guian Li, and as a doctoral student under the
6042–6108.
supervision of Professor Harong Zheng. Moreover, she is a MD-PhD student. Her
[13] M. Salmistraro, A. Schwartzberg, W. Bao, L.E. Depero, A. Weber-Bargioni, S.
research interest focuses on the fluorescence spectroscopy of noble metal materials
Cabrini, I. Alessandri, Triggering and monitoring plasmon-enhanced reactions
and rare earth materials.
by optical nanoantennas coupled to photocatalytic beads, Small 9 (2013)
3301–3307. Chengyun Zhang is a twice year master student in the group of the Optics major,
[14] B. Chowdhury, J.J. Bravo-Suárez, N. Mimura, J.Q. Lu, K.K. Bando, S. Tsubota, M. working on the surfaced enhanced fluorescence spectroscopy.
Haruta, In situ UV–vis and EPR study on the formation of hydroperoxide
species during direct gas phase propylene epoxidation over Au/Ti-SiO2 Wei Gao received his doctoral degree (2015) in Optics major from the Shaanxi
catalyst, J. Phys. Chem. B 110 (2006) 22995–22999. Normal University, working on the fluorescence properties of rare earth materials.
[15] G. Richner, J.A. Bokhoven, Y.M. Neuhold, M. Makosch, K. Hungerbühler, In situ
infrared monitoring of the solid/liquid catalyst interface during the Zhihang Han a sophomore student from the Shaanxi Normal University, working
three-Phase hydrogenation of nitrobenzene over nanosized Au on TiO2 , Phys. on the development of noble metal materials.
Chem. Chem. Phys. 13 (2011) 12463.
Tingzhuo Liu is graduated in the Shaanxi Normal University and received his master
[16] M.T. Sun, H.X. Xu, Novel application of plasmonics: plasmon-driven
degree in 2014.
surface-catalyzed reactions, Small 8 (2012) 2777–2787.
[17] Z.L. Zhang, T. Deckert-Gaudig, V. Deckert, Label-free monitoring of plasmonic Caixia Li is a twice year master student in the group of the Optics major. Her research
catalysis on the nanoscale, Analyst 140 (2015) 4325. interest focuses on the theoretical analysis for noble metal materials.
614 Q. Han et al. / Sensors and Actuators B 231 (2016) 609–614

Zhaojin Wang is a twice year doctor student in the group of the Optics major, Hairong Zheng is a professor School of Physics and Information Technology, Shaanxi
working on the fluorescence properties of rare earth materials. Normal University. She received her Ph.D. degree from Department of Physics &
Astronomy, The University of Georgia in 2003. She did her post-doctoral research
Enjie He received his doctoral degree (2014) in Optics major from the Shaanxi Nor- in the University of Georgia Athens and Clemson University. Her research interests
mal University, working on the surfaced enhanced fluorescence properties of rare include Laser spectroscopy, excited state dynamics, optical properties of nanoma-
earth materials. terials, and surface enhanced spectroscopy, etc.