Plasmon-Exciton Coupling Interaction for Surface Catalytic ...download.xuebalib.com/4c738MWrPAdz.pdf · Keywords: Plasmon-exciton coupling, MoS 2, Ag nanoparticles, graphene, TiO

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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

Chem. Rec. 2018, 18, 481–490 © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 481

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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.

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


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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]



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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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Figure 11. a) The substrate for the contrast experiments and the SERSspectra are shown. There are only Ag NPs on the left, while the Ag NPs arecovered by MoS2 on the right. b) The surface catalytic reactions for the25 nm Ag NPs with MoS2 (black line) and without MoS2. (red line).

[56]

Figure 12. (a) SERS spectra of surface catalytic reactions of PATP to DMABon the different AgNPs-TiO2 film hybrids with UV irradiation time for 2, 5,15, 30, and 60 min. (b) Laser wavelength-dependent SERS spectra of theconversions on 15 min AgNPs-TiO2 film hybrid. (c) Relative intensity ofRaman band at 1437 cm�1 of the conversions of PATP to DMAB on AgNPs-TiO2 film hybrids compared to that at 1071 cm

�1, measured in atmosphereenvironments, plotted as a function of excitation wavelengths.[68]



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Received: August 13, 2017Accepted: October 2, 2017Published online on October 16, 2017



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Plasmon-Exciton Coupling Interaction for Surface Catalytic ...download.xuebalib.com/4c738MWrPAdz.pdf · Keywords: Plasmon-exciton coupling, MoS 2, Ag nanoparticles, graphene, TiO