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Plasmon-Exciton Coupling Interactionfor Surface Catalytic
Reactions
Jingang Wang+,[a, c] Weihua Lin+,[b] Xuefeng Xu+,[b] Fengcai
Ma,[c] and Mengtao Sun*[b]
Personal Account
T H EC H E M I C A L
R E C O R D
DOI: 10.1002/tcr.201700053
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Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley
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Abstract: In this review, we firstly reveal the physical
principle of plasmon-exciton couplinginteraction with steady
absorption spectroscopy, and ultrafast transition absorption
spectroscopy,based on the pump-prop technology. Secondly, we
introduce the fabrication of electro-opticaldevice of
two-dimensional semiconductor-nanostructure noble metals hybrid,
based on theplasmon-exciton coupling interactions. Thirdly, we
introduce the applications of plasmon-excitoncoupling interaction
in the field of surface catalytic reactions. Lastly, the
perspective of plasmon-exciton coupling interaction and
applications closed this review.
Keywords: Plasmon-exciton coupling, MoS2, Ag nanoparticles,
graphene, TiO2
1. Introduction
Surface plasmons (SPs) is the collective electrons
oscillatoralong the interface between noble metals and dielectric,
whenthe light radiates on the surface of noble metals.[1] There
aretwo kinds of surface plasmons: the local SPs (LSPs)
andpropagating SPs (PSPs). Based on the LSP resonance
(LSPR),surface-enhanced Raman scattering (SERS) and
Tip-enhancedRaman scattering (TERS) spectra have been widely
applied inthe field of ultrasensitive Raman analysis at
nanoscale.[2–15]
SPs, coupled with photons, can act as a collective excitationof
conduction electrons that propagate in a wave-like manneralong an
interface between a metal and a dielectric, known asSP polaritons
(SPPs).[16] The propagating SPPs (PSPPs) hasalso been used to the
remote Raman detection, known asRemote-excitation of
surface-enhanced Raman scattering(RE-SERS),[17–20] and there are
many advantages over thelocal excited SERS. Since 2010, the surface
plasmons havebeen used in the field of surface catalytic
reactions,[21–25] basedon the plasmonic hot electrons generated
from plasmondecay, and the lifetime of hot electrons are around
onehundred femtoseconds. SERS, electrochemical SERS, TERS,and
RE-SERS spectra are usually used for the monitor ofsurface
catalytic reactions in atmosphere, liquid and high-vacuum
environments.[26–45] The plasmon-driven chemicalreactions are of
great advantages over the traditional chemicalreactions based on
the thermal effect. While the short lifetimeof plasmonic hot
electrons around one hundred femtosecond,and the low efficiency of
photon-to electrons limit the fully
developments of plasmonic chemistry. The history anddevelopments
of plasmon-driven surface catalytic reaction canrefer recent
published review papers.[46–50]
The concept of excitons was firstly proposed by Frenkel
in1931.[51] An exciton, as an electrically neutral quasi-particle,
isthe bound state of a hole and an electron, which are attractedto
each other by the electrostatic Coulomb force. The excitoncan
transfer energy without transporting net electric charge
insemiconductors, some liquids and insulators.[52,53] The decayof
the exciton is limited by resonance stabilization because ofthe
overlap between the electron and hole wave functions,which results
in the lifetime of the exciton being extended.Thr excitons, TiO2
nanoparticles, and transition metaldichalcogenides (TMDCs) at
nanoscales[54] have been success-fully applied in the field of
photoinduced surface catalyticreactions[55] due to their unique
properties, such as largesurface-to-bulk ratios and quantum
confinement effects.While, the efficiency and probability of
catalytic reactionsusing these materials have been compromised due
to theirlarge band gaps and the low yield of hot electrons.
One promising method for solving above problems ofplasmons or
exciton driven catalytic reactions is hybrid thesematerials between
plasmonic metals and excitonic semi-conductors.[56–68] The cover of
the two dimensional semi-conductors on the plasmonic nanostructures
can avoid thequickly oxidation of the metals, such as silver. The
hybridstructures may lead to a decreased band gap, an
adjusteddensity of states (DOS) and prolonged lifetimes for the
hotelectrons.[50,64] Furthermore, SPR can significantly increasethe
cross-section for light absorption in excitonic materialsthrough a
locally confined electromagnetic fieldenhancement. The plasmon and
exciton coupling interactionshave greatly promoted the
plasmon-exciton co-driven chem-ical reactions, confirmed by recent
experimental reports.[56–68]
The fabrication of substrates and devices, based on the hybridof
noble plasmnic nanostructures and the excitonic semi-conductors, is
another important topic in the field ofplasmon-exciton co-driven
surface catalytic reactions. Withthe help of plasmon-exciton
coupling interaction, thesensitivity of detection can be enormously
enhanced and thepotential application can be extended. Beside,
except for thehybrid systems that mentioned in the paper, there are
various
[a] J. Wang+
College of Science, Liaoning Shihua University, Fushun,
113001,China[b] W. Lin,+ X. Xu,+ M. SunBeijing Key Laboratory for
Magneto-Photoelectrical Composite andInterface Science, Center for
Green Innovation, School of Mathe-matics and Physics, University of
Science and Technology Beijing,Beijing, 100083, ChinaE-mail:
[email protected][c] J. Wang,+ F. MaDepartments of Physics,
Liaoning University, Shenyang, 110036,China[+] Contributed
Equally.
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materials that are suitable to induce plasmon-exciton
couplinginteraction.[69–71] Therefore, it is very necessary to
compre-hend the internal mechanism and tap the potential
advantagesof plasmon-exciton coupling interaction.
In this review, we firstly introduce the physical principleof
plasmon-exciton coupling interactions, and then, thefabrication of
hybrid substrate or device, based on the hybridof plasmonic and
excitonic nanostructures. Thirdly, weintroduce plasmon-exciton
co-driven surface catalytic reac-tions. Lastly, we close the review
with the perspective ofplasmon-exciton coupling interaction in the
fields of surfacecatalytic reactions, using different spectral
analysis methods.
2. Principle of Plasmon-Exciton CouplingInteractions
2.1. Monolayer Graphene-Ag Nanoparticles HybridSystem
Graphene and Ag nanostructures have been hybrids andsuccessfully
applied in plasmon-graphene co-driven chemicalreactions, but the
mechanism has not been clearly elucidatedyet. For examples, what is
the time scale of the dynamic
process of the plasmon-induced hot electrons transferring
tographene? How the hybrid system can significantly increasesthe
efficiency of the catalytic reaction? Ding et al., havedesigned a
series of experiments to answer these questions(see Figure 1).[64]
Firstly, they fabricated graphene-Ag nano-wire hybrid, which is
shown in Figure 1(a). We can see thereis a single Ag nanowire
covered with graphene. Then theycarried out measurements of
ultrafast transient absorptionspectroscopy (Figure 1(b)-(e)). The
fitted curve in Figure 1cindicates that the lifetime of
plasmon-induced hot electronsinteracting with phonons in graphene
is about 3.2�0.8 ps,which is significantly longer than that of
isolated Ag nanowire(150 fs). These results demonstrate that
graphene can stronglyharvest hot electrons generated from Ag
plasmon decay,which can not only lead to a significant accumulation
of highdensity hot electrons, but also prolong the lifetime of
thesehot electrons from femtosecond to picosecond.
2.2. Monolayer MoS2-Ag Nanoparticles Hybrid System
TMDCs are a series of materials with the formula MX2,[89]
where M is a transition metal element from group IV (Ti, Zr,Hf
and so on), group V (for instance V, Nb or Ta) or group
Jingang Wang is a Ph.D. candidate super-vised by Prof. Fengcai
Ma and Prof.Mengtao Sun at the Department ofChemistry and Physics,
Liaoning Univer-sity, China. His current research interestsare the
properties and applications of two-dimensional (2D) materials and
plasmon-driven surface catalytic reactions.
Weihua Lin is a PhD candidate under thesupervised by Prof.
Mengtao Sun at Bei-jing Key Laboratory for Magneto-Photo-electrical
Composite and Interface Science,School of Mathematics and Physics,
TheUniversity of Science and Technology Bei-jing. Her current
research interests focuson electrochemical SERS,
supercapacitors,and plasmon-driven surface catalytic
reac-tions.
Xuefeng Xu is a PhD candidate under thesupervised by Prof.
Mengtao Sun at Bei-jing Key Laboratory for Magneto-Photo-electrical
Composite and Interface Science,School of Mathematics and Physics,
TheUniversity of Science and Technology Bei-jing. Her current
research interests focus
on electrochemical SERS and plasmon-driven surface catalytic
reactions.
Mengtao Sun obtained his Ph.D. in 2003from the State Key
Laboratory of Molec-ular Reaction Dynamics, Dalian Instituteof
Chemical Physics, Chinese Academy ofSciences (CAS). From 2003 to
2006, heworked as a postdoc at the Department ofChemical Physics,
Lund University. Since2006, as an associate professor, he hasworked
at the Beijing National Laboratoryfor Condensed Matter Physics,
Institute ofPhysics, CAS. In 2016, he became a FullProfessor in
University of Science andTechnology Beijing, China. His
currentresearch interests focus on two dimen-sional(2D) materials
and plasmonics, aswell as the exciton-plasmon couplinginteraction
for surface catalytic reaction.ResearcherID: B1131-2008.
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VI (Mo, W and so on), and X is a chalcogen (S, Se or Te). Asone
of the typical TMDCs, MoS2 is composed of covalentlybonded S�Mo-S
sheets that are bound by weak van der Waalsforces. In its bulk
form, MoS2 is a semiconductor with anindirect bandgap of about 1.29
eV, while it turns to be directbandgap of 1.88 eV for the
monolayer. In monolayer (1 L)MoS2, there are three well-defined
peaks at 1.9 eV, 2.1 eV (‘A’and ‘B’) and a broad peak ‘C’ at 2.9
eV, see Figure 2(a). Thepeaks A and B are attributed to optical
absorption by band-edge excitons, and the peak C to absorption by
excitonsassociated with the van Hove singularity of MoS2.
Comparedwith the traditional 2D material-graphene, MoS2 has a
strongexciton effect. It has been shown that hybridizing
monolayerMoS2 with metal nanostructures results in various degrees
ofexciton-plasmon coupling and correspondingly enhanced
light absorption and emission. For example, Yang, et
al.,recently hybridized the MoS2 with different sizes of
Agnanoparticles (see Figure 2),[56] and they found the
plasmon-exciton coupling can be tuned in monolayer
MoS2-Agnanoparticles hybrid systems by tune the sizes of the
Agnanoparticles. With the increase of the size of Ag
nano-particles, the absorption peak of plasmon-excition
couplinginteraction gradually red shifted, as well as
absorptionintensities, which demonstrate the degree of
plasmon-excitoncoupling interaction can be well manipulated.
Furthermore,the stronger plasmon-exciton coupling interaction can
bedemonstrated on the plasmon-enhanced fluorescence, seeFigure 3.
It is found that with the increase of Ag nanoparticlesizes, the
photoluminescence (PL) of monolayer MoS2 can besignificantly
enhanced up to more than 50 times. Theseresults revealed that SPR
can significantly increase the cross-section for light absorption
in TMDC nanostructuresthrough a locally confined field enhancement
(gexc/ jE j 2,where gexc is the excitation rate), due to collective
electronsoscillation of plasmon resonance.
2.3. TiO2 Nanoparticles-Ag Nanoparticles Hybrid System
To study the plasmon-exciton coupling interaction,
steadyspectroscopy and ultrafast pump-probe absorption
spectro-scopy were studied experimentally. Ding firstly
synthesizedthe TiO2 film on the quartz, where the thickness of the
nano-sized TiO2 film was calculated to be approximately 208 nm,and
the absorption peak is around 524 nm. And then, Dingsynthesized the
Ag nanoparticles with different sizes on the
Figure 1. SEM imaging of a single Ag nanowire veiled with
monolayergraphene and ultrafast pump-probe transient absorption
spectroscopy. (a)SEM image of a single Ag nanowire coated by
monolayer graphene. (b)Ultrafast pump-probe transient absorption
spectroscopy of hybrid graphene-Ag nanowire excited by 400 nm
laser. (c) The fitted dynamic curve at532 nm. (d) Ultrafast
pump-probe transient absorption spectroscopy ofhybrid graphene-Ag
nanowire in NIR region. (e) The fitted dynamic curve at1103
nm.[64]
Figure 2. (a) The transmission spectra of Ag NPs (6.1 nm),
monolayer MoS2and MoS2/Ag NPs hybrids on quartz substrates; b) the
transmission spectraof Ag NPs, where the average diameters of Ag
NPs are 6.1, 14.5 and 25 nmrespectively; c) the transmission
spectra of MoS2/Ag NPs hybrids withdifferent thicknesses of Ag NPs;
d) The absorbance for three kinds of hybridsat 532 nm.[56]
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TiO2 film, see Figure 4(a)-(e), where the inset in Figure 4(e)is
the XRD spectrum of Ag nanoparticles. In the absorptionspectra in
Figure 4(f ) demonstrated the plasmon-excitoninteraction of TiO2
film with Ag nanoparticles with differentsizes. It is clearly
observed that there is a broad absorptionband in the spectra, which
results from the nonuniformity ofAg nanoparticles. Because of the
broad absorption peak ofAgNPs-TiO2 film hybrids, the plasmon peak
of Ag can beeasier to superpose with the exciton peak of TiO2,
resultingin the strong plasmon-exciton coupling.It is found
thatexciton peak of TiO2 film around 523 nm are coupled withtwo
plasmon peaks around 420 nm and gradually red-shifted
with the increase of Ag nanoparticles sizes. For the case
inFigure 4(c), there are strongest plasmon-exciton couplingaround
532 nm.
Also, the ultrafast transfer process of plasmon-induced
hotelectron from Ag nanoparticles into TiO2 nanoparticles
wasinvestigated by femtosecond transient absorption spectro-scopy.
Ding prepared the TiO2 nanoparticles-Ag nano-particles hybrid
system.[68] Figure 5(a) show the SEM imagesof AgNPs grown on
nano-sized TiO2 film under UVirradiation time for 2 min.
Plasmon-exciton coupling ofAgNPs-TiO2 film hybrids has been
revealed with ultrafasttransient absorption spectroscopy. Figure
5(b) shows thetransient absorption spectrum of AgNPs-TiO2 film,
whereAgNPs were synthesized within 2 minutes. It is found thatthere
are two ultrafast absorption peaks around 475 nm and532 nm. The
lifetime of electron-electron interaction is 2 ps,and the lifetime
of electron-phonon interaction is 71 ps,which provide high kinetic
energy and thermal energy for thecatalytic reactions,
respectively.
3. Plasmon-Exciton Co-Driven Surface CatalyticReactions
3.1. Graphene-Plasmonic Nanostructure Hybrid forSurface
Catalytic Reactions
3.1.1. Graphene-Ag Bowtie Nanoantenna Arrays Hybrids
Since it was discovered in 2004, graphene, a single atomiclayer
of graphite, has attracted vast interests due to its
uniqueproperties. Recently, Dai and coworkers reported that
thenumber of graphene layers could control the
plasmon-drivensurface-catalyzed reaction,[57] where
para-aminothiophenol(PATP) was oxidized to p,p-dimercaptoazobenzene
(DMAB)on graphene-coated Ag bowtie nanoantenna arrays
(ABNA)hybrids, where graphene-ABNA hybrids is shown in Figure
6.Figure 6(a) is a schematic view of the
graphene-assisted,plasmon-driven reaction of the transformation of
PATP-to-DMAB. Figure 6(b) is the SEM of graphene covered ABNA
Figure 3. (a-c) The photoluminescence (PL) spectrum of MoS2
enhanced bylocal surface plasmon resonance, where the average
diameters of the Ag NPsare 6.1, 14.5 and 25 nm respectively; d) The
enhancement factors fordifferent thicknesses.[56]
Figure 4. SEM images of Ag nanoparticles deposited on the
nano-sized TiO2film in 3 mM AgNO3 solution after UV irradiation for
(a) 2, (b) 5, (c) 15,(d) 30, and (e) 60 min. (f ) In-situ real-time
UV-visible absorbance spectra ofAg nanoparticles grown on
nano-sized TiO2 film under UV irradiation for 2,5, 15, 30 and 60
min, respectively.
Figure 5. (a) SEM images of Ag nanoparticles deposited on the
nano-sizedTiO2 film in 3 mM AgNO3 solution after UV irradiation for
2 min, (b)Three-dimensional transient absorption spectrum for
AgNPs-TiO2 filmhybrids synthesized within 2 min.[68]
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hybrids. Figure 6(c) shows the bare Ag bowtie nanoantennaarrays.
From Figure 6(d)-(e), we can see the bare ABNA areoxidized after a
month, while the graphene-covered ABNAshows no signs of changes in
the same period. Then, theysystematically studied the
plasmon-driven surface-catalyzedreactions on this kind of hybrid,
and found out thatmonolayer graphene can further enhance the
reaction, whilebilayer graphene decreased the probability of the
PATP-to-DMAB conversion, see Figure 7. This is because
monolayer
graphene introduces a strong dipole, enhanced by the EMfields,
which allows electron transition between PATP andgraphene; then, a
couple of the PATP molecules lose electronsto become DMAB molecules
on the graphene surface. Forthe bilayer graphene, the electron
transition is weak and hotelectron transfer from Ag is relative
difficult than that in thecase of monolayer graphene.
3.1.2. Three Dimensional Graphene-Ag NanoparticlesHybrids
The reported graphene-Ag nanostructure hybrids can
signifi-cantly enhance the surface catalytic reactions, but as
twodimensional (2D) systems, have some limitations such asfrangible
surface, low surface-to-volume and only single sidecomposited with
nanoparticles, etc. Therefore, 3D hybridmay be a much better
selection than 2D hybrid, because ithas a three-dimensional space
with free spatial orientation,high surface-to-volume and two-sided
composited with nano-particles. Zhao and coworkers have
successfully fabricated a3D hierarchical hybrid of vertical
flower-like graphene nano-sheets (FGNSs) sandwiched by Ag
nanoparticles (Ag-NPs),[58]
and the hybrid was grown on silicon nanocone arrayssubstrate
(see Figure 8(a)-(d)).Then they studied the surfacecatalytic
reactions of 4NBT on these kinds of 2D and 3Dgraphene-Ag
nanoparticles hybrids (see Figure 8e). Throughcomparing the
intensity ratio of DMAB peak at 1432 cm�1
to the D peak of graphene at 1335 cm�1, they found 3Dstructure
of graphene/Ag-nanoparticles is much more efficientfor enhancing
plasmon-driven catalytic reactions than 2Dplane structure. Note
that the size and distribution of Agnanoparticles on the graphene
nanosheet can influence thefrequency of local surface plasmon
resonance.
3.1.3. Graphene-Ag Nanoparticles Hybrid inElectrochemical SERS
in Liquid
Wang and coworkers.,[62, 63] studied surface catalytic
reactionsco-driven by plasmon-excition coupling in liquid, where
theFermi Level of the hybrid of graphene-roughened Agelectrode were
controlled by potentials in electrochemicalSERS.62 The roughened Ag
electrode without and withgraphene can be seen from Figure 9, where
the clear graphenecircled by red color can be seen from Figure
9(b). Withoutthe graphene, the electrochemical SERS spectrum
showedthat when the potential is �0.4 V, the surface
catalyticreaction occurred, where the p-nitroaniline (PNA)
wasreduced to 4,4’-diaminoazobenzene (DAAB), see Figure 9(c);while
when the graphene is covered on the roughened Agelectrode, the
surface catalytic reaction happened withoutadding potential, see
G-SERS in Figure 9(d). When the laseris changed from 532 nm to 785
nm, and the other parameters
Figure 6. (a) Schematic view of graphene-assisted,
plasmon-driven reaction ofthe transformation of PATP-to-DMAB. (b)
Scanning electron microscopic(SEM) image of the large-area,
well-ordered, uniform-sized, graphene-coatedAg bowtie nanoantenna
arrays (below the yellow dashed line); the yellowdashed line shows
the graphene border. (c) SEM image of bare Ag bowtienanoantenna
arrays. (d) SEM images of the bare Ag bowtie nanoantennaarrays and
(e) chemically inert, graphene covered Ag nanoantenna arrays aftera
month. The Ag bowtie nanoantenna arrays are protected by the
graphenemonolayer.[57]
Figure 7. In situ SERS of PATP on (a) ABNA, (b) 1G-coated ABNA,
(c)2G-coated ABNA. (d) The relationship between the reaction rate
and theirradiation time for ABNA (black line), 1G-coated ABNA (red
line), and 2G-coated ABNA (blue line).[57]
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are fixed, the influence of plasmon-exciton coupling on theFermi
level of hybrid system is revealed, where the Fermi levelof hybrid
system is changed 0.45 V in G-SERS, comparedwith the Fermi level of
roughened Ag electrode in SERS.
The physical mechanism can be seen from Figure 9(e).The relation
between the shift of electric potential thatapplied on the
electrode and optical absorption energy can bedescribed as:[72]
EðDVÞ ¼ EðDV ¼ 0Þ-ebDV ð1Þ
where the E(~V) is the optical absorption energy and the ~Vis
the amount of change in the electric potential V. Besides,the b�1
and in the Helmholtz model b =1. When theincident laser is 532 nm,
the E(~V=0) =2.33 eV, and with
the help of electric potential of �0.4 V, the
plasmon-drivenchemical reaction can occur. The electric potential
of �0.4 Vis borrowed from the cyclic voltammogram. By using
theequation (1), it can be found that the
E(~V=�0.4)=2.33-eb(�0.4)=2.74 eV, which means the wavelength of
opticalabsorption is 446 nm. This wavelength of optical
absorptionwould be large enough to excite the localized surface
plasmonresonance (LSPR) of roughened Ag substrate for
surfacecatalytic reaction of PNA to DAAB. The E(~V=0) =1.579 eV,
and the plasmon-exciton co-driven chemicalreaction with 785 nm
laser can occur at ~V=�>0.7 V.With the contribution of graphene,
the optical energy mustreach the barrier, which is equal to the
E(~V=�0.7)=2.279 eV. Comparing with the SERS of PNA excited at532
nm, it can be found out that the Fermi level of hybridsystem had
been increased about 0.451 eV, which iscontributed by graphene. So,
we can confirm that theplasmon-exciton coupling interaction can
increase the FermiLevel of hybrid system, compared with the Fermi
level ofroughened Ag electrode; which can significantly decrease
thereaction barrier of the reduced reactions, and
significantlyincrease the efficiency of surface catalytic
reaction.
3.2. TMDCs-Ag Nanoparticles Hybrids for SurfaceCatalytic
Reactions
Yang and coworkers studied the monolayer MoS2-Ag nano-particles
hybrids for surface catalytic reaction,[56] where 4NBTwas reduced
to DMAB. Transmission spectra in Figure 2 andfluorescence spectra
in Figure 3 have revealed the size of Agnanoparticles can well
manipulate the plasmon-excitoncoupling interactions, where the
transmission spectra aregradually red shifted with the increase of
size of Agnanoparticles, as well as the increase of transmission
intensity.The Ag nanoparticle size dependent plasmon-exciton
co-driven surface catalytic reactions can be seen from Figure 10,it
is found that for the strongest plasmon-exciton couplingnear 532 nm
in Figure 10, the efficiency and probability ofsurface catalytic
reaction is best, see Figure 10(f ), where theRaman peak of 4NBT at
1342 cm�1 is quickly decreased,while the Raman peak of DMAB is
significantly increased,where the Raman peaks of MoS2 around 400
cm
�1 issignificantly decreased. Usually, the most important
Ramanpeaks of organic molecules are from 1000 to 1700 cm�1,while
all of Raman peaks below 500 cm�1 for the MoS2,which is an
important advantages for the SERS detectionwithout Raman background
from substrate in the range from1000 to 1700 cm�1.
To confirm the superiority of plasmon-exciton co-drivensurface
catalytic reactions, the contrast experiments onsubstrates with and
without the cover of MoS2 wereperformed, see Figure 11. Although
the MoS2 layer weakens
Figure 8. SEM images of (a) silicon nanocone array, which were
fabricatedby the maskless etching in the ICP system, (b) the
floral-clustered graphenenanosheets, which were grown on the
nanocone array with the growth timesof 30 minutes, (c) the
high-resolution image of petaliform graphenenanosheets on the
nanocone tips, (d) Ag nanoparticles attached to both sidesof a
graphene nanosheet, (e) the schematic of three different substrates
(leftside) corresponding to their SERS spectra (right
side).[58]
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the electric field by approximately 30 %, the efficiency of
theplasmon-exciton co-driven surface catalytic reaction at lowlaser
intensities increases.
One of the most important reason is that hot electronsgenerated
from plasmon decay rapidly transferred to mono-layer MoS2, there is
another important contribution thatMoS2 is excited directly by LSPR
effect to generate chargecarriers. The carrier-carrier interaction
plays important role insurface catalytic reaction, and the
carrier-photon interactioncan convert to thermal energy for surface
catalytic reaction.
3.3. Ag Nanoparticles-TiO2 Film Hybrids Studied bySERS
Spectroscopy
Ding and coworkers reported Ag nanoparticles-TiO2 filmhybrids
driven surface catalytic reactions.[68] The typicaloxidation
reactions of PATP dimerized to DMAB werestudied on AgNPs-TiO2 film
hybrids under UV irradiationfor 2, 5, 15, 30 and 60 min. As shown
in Figure 12(a), theconversions of PATP (5310�5 M) into DMAB can be
clearlyobserved on all AgNPs-TiO2 film hybrids, where the
Ramanbands appeared at 1142, 1389 and 1437 cm�1 are attributedto
the ag modes of DMAB. Moreover, these reactions can befinished
within the exposure time of 1 s, which implies theconversions are
so fast that no intermediate reaction processcan be observed. The
SERS intensity of the reactions on15 min AgNPs-TiO2 film has a
maximum. This phenomenonfurther confirms the strongest coupling
occurred in 15 minAgNPs- TiO2 film hybrid. Note that, the following
SERSspectra were conducted on the 15 min AgNPs-TiO2 filmhybrid.
The effect of excitation wavelength on the oxidationreactions of
PATP on 15 min AgNPs-TiO2 film has also beeninvestigated. Figure
12(b) illustrates the SERS spectra forPATP using excitation sources
of 532, 632.8 and 785 nm,respectively. Notably, the conversions of
PATP to DMABwere observed in all the spectra. The band appeared
at1071 cm�1 is assigned to a1 mode of PATP, and that appearedat
1437 cm�1 is assigned to ag mode of DMAB. Thus, the1437:1071 cm�1
intensity ratio can be used to probe theproduct conversion. As
shown in Figure 12(c), the intensityratio was evaluated against the
excitation wavelength.Evidently, as the excitation wavelength
decreases, the bandintensity of at 1437 cm�1 increases with respect
to the bandat 1071 cm�1. The higher yield of product excited at 532
nmnot only results from the excitation laser wavelength closer
tothe SPR peak of AgNPs, but also arises from the
strongplasmon-exciton coupling.
Figure 9. (a) and (b) The SEM image of the roughened Ag
substrate withoutand with graphene, and the scale bar is 500 nm.
(b) and (c) plasmon-excitonco-driven surface catalytic reaction
excited at 532 nm and 785 nm.[62] (e)Schematic diagram of
plasmon-exciton co-driven surface catalytic reaction at532 nm and
785 nm.[62]
Figure 10. (a-c) SEM images of MoS2/Ag NPs on SiO2/Si
substrates, wherethe average diameters of the Ag NPs are 6.1, 14.5
and 25 nm respectively; d-f ) laser power dependent SERS spectra of
the MoS2/Ag NPs hybridscorresponding to Figure 9a-c.[56]
P e r s o n a l A c c o u n t T H E C H E M I C A L R E C O R
D
Chem. Rec. 2018, 18, 481–490 © 2018 The Chemical Society of
Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley
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4. Conclusion
In this review, we revealed physical mechanism of
plasmon-exciton coupling interaction, and summarized recent
reportedexperiments and their applications in plasmon-exciton
co-driven surface catalytic reactions. It is found that
theplasmon-exciton co-driven surface catalytic reaction is
muchbetter than that driven by plasmon alone. In future,
furtherdeeper understanding on physical mechanism of
plasmon-exciton coupling interactions can promote potentially
appli-cations in the fields of sensor, catalytic reaction, energy
andenvironments.
Acknowledgements
This work was supported by National Natural ScienceFoundation of
China (Grant No. 11374353, 91436102 and11274149), National Basic
Research Program of China(Grant number 2016YFA02008000), Municipal
Science andTechnology Project (No. Z17111000220000), and theProgram
of Liaoning Key Laboratory of Semiconductor LightEmitting and
Photocatalytic Materials.
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