Photocatalytic activity enhanced by plasmonic resonant energy transfer from metal to semiconductor

Plasmonic metal nanostructures have been incorporated into semiconductors to enhance the solar-light harvesting and the energy-conversion efficiency. So far the mechanism of energy transfer from the plasmonic metal to semiconductors remains unclear. Herein the underlying plasmonic energy-transfer mechanism is unambiguously determined in Au@SiO(2)@Cu(2)O sandwich nanostructures by transient-absorption and photocatalysis action spectrum measurement. The gold core converts the energy of incident photons into localized surface plasmon resonance oscillations and transfers the plasmonic energy to the Cu(2)O semiconductor shell via resonant energy transfer (RET). RET generates electron-hole pairs in the semiconductor by the dipole-dipole interaction between the plasmonic metal (donor) and semiconductor (acceptor), which greatly enhances the visible-light photocatalytic activity as compared to the semiconductor alone. RET from a plasmonic metal to a semiconductor is a viable and efficient mechanism that can be used to guide the design of photocatalysts, photovoltaics, and other optoelectronic devices.     

Nanostructured materials with localized surface plasmon resonance for photocatalysis

Localized surface plasmon resonance（LSPR） enhanced photocatalysis has fascinated much interest and considerable efforts have been devoted toward the development of plasmonic photocatalysts.In the past decades,noble metal nanoparticles（Au and Ag） with LSPR feature have found wide applications in solar energy conversion.Numerous metal-based photocatalysts have been proposed including metal/semiconductor heterostructures and plasmonic bimetallic or multimetallic nanostructures.However,high cost and...     

Plasmonic photoelectrochemical reactions on noble metal electrodes of nanostructures

Plasmonic noble metal nanostructures have been targeted due to their strong surface plasmon resonance at photoelectrochemical interfaces. Recently, it has been concluded that, the plasmonic noble metal nanostructures on photoexcitation permit the transfer of effective hot carriers (hot electron/hole pair) to nearby adsorbed molecules where, the transformed hot carriers can efficiently decrease the activation barrier of a reaction. In this review, our recent achievements in the plasmon-mediated chemical reactions of organic molecules such as para-aminothiophenol, substituted para-aminothiophenol and para-nitrothiophenol at nanostructures modified noble metal electrodes using surface enhanced Raman spectroscopy, electrochemical methods, and theoretical calculations will be discussed.     

Mechanistic Studies of Plasmon Chemistry on Metal Catalysts

Chemical reactions induced by the localized surface plasmon (LSP) of metal nanostructures could be important for a sustainable society to achieve highly efficient conversion from solar energy to chemical energy. However, the reaction mechanism of plasmon chemistry in metal catalysis is still controversial. Mechanistic studies of plasmon chemistry involving direct interactions between the LSP and molecules are reviewed and discussed in terms of the excitation mechanisms of the molecules. We focus on the studies performed using plasmonic metal nanoparticles and highlight the recent progress in plasmon chemistry investigated using scanning probe microscopy with high spatial resolution to obtain mechanistic insights that cannot be obtained by macroscopic analytical methods. This Minireview delivers an overview of the mechanistic understanding of plasmon chemistry in metal catalysis at the current stage, and provides guidance for future studies with respect to clarifying reaction mechanisms.     

Designer Gold-Framed Palladium Nanocubes for Plasmon-Enhanced Electrocatalytic Oxidation of Ethanol

Surface plasmon of coinage metal nanostructures has been employed as a powerful route in boosting the performances in heterogenous catalysis. Development of efficient plasmonic nanocatalysts with high catalytic performance and efficient light harvesting properties is of vital importance. Herein, we rationally designed and synthesized a plasmonic nanocatalyst composed of Au-framed Pd nanocubes by an Ag(I)-assisted seed-mediated growth method. In the synthesis, the incorporation of Ag(I) suppresses the reduction of Au on the {100} surface of cubic Pd seeds and leads to the formation of Au nanoframes on the Pd nanocubes. The unique Au-framed Pd nanocubes can integrate the superior electrocatalytic of Pd and the outstanding plasmonic properties of Au. Thus, these nanostructures were employed as plasmonic nanocatalysts for plasmon-enhanced electrocatalytic oxidation of ethanol with improved stability.     

Quenching of TiO2 photo catalysis by silver nanoparticles

The plasmon resonance of metal nanostructures affects neighboring semiconductors, quenching or enhancing optical transitions depending on various parameters. These plasmonic properties are currently investigated with respect to topics such as photovoltaics and optical detection and could also have important consequences for photocatalysis. Here the effect of silver nanoparticles of a size up to 30 nm and at maximum 0.50 monolayers on the photocatalytic oxidation of ethylene on TiO₂ is studied. Since the plasmon resonance energy of silver nanoparticles is comparable with the TiO₂ band gap, dipole-dipole interaction converts excitons into heat at the silver nanoparticle. This indicates that plasmonic interaction with TiO₂ semiconductor catalysts can reduce the photo catalytic activity considerably.     

Core-satellites assembly of silver nanoparticles on a single gold nanoparticle via metal ion-mediated complex

We report core-satellites (Au-Ag) coupled plasmonic nanoassemblies based on bottom-up, high-density assembly of molecular-scale silver nanoparticles on a single gold nanoparticle surface, and demonstrate direct observation and quantification of enhanced plasmon coupling (i.e., intensity amplification and apparent spectra shift) in a single particle level. We also explore metal ion sensing capability based on our coupled plasmonic core-satellites, which enabled at least 1000 times better detection limit as compared to that of a single plasmonic nanoparticle. Our results demonstrate and suggest substantial promise for the development of coupled plasmonic nanostructures for ultrasensitive detection of various biological and chemical analytes.     

Designing caps for colloidal Au nanoparticles

The plasmonic property of a nanostructure is highly dependent on its morphology, but there are few methods for appending a domain as the “functional group” or modifier. As a means of modulating plasmonic properties, we create and modulate Au hats on Au nanoparticles, including mortarboards, beret hats, helmets, crowns, antler hats and antenna hats. The structural control arises from the active surface growth as a result of dynamic competition between ligand absorption and metal deposition. It allows the continuous tuning of hat morphologies, from the facet-controlled growth of mortarboards, to the spreading-favored growth of beret hats and helmets, and to the vertical growth of pillars in crowns, antler hats and antenna hats. Among these plasmonic nanostructures, the mortarboards show excellent SERS enhancement of 8.1 × 10⁵, which is among the best in colloidal nanostructures; and the antler hats show the photothermal conversion efficiency of 66.2%, which compares favorably with the literature reports.

We show that active surface growth is an effective method to create structural variety in the appending domain of Au seeds. The dynamic competition between the growth sites led to different Au hats on seeds.     

Plasmonic Titanium Nitride Tubes Decorated with Ru Nanoparticles as Photo-Thermal Catalyst for CO2 Methanation

Photo-thermal catalysis has recently emerged as a viable strategy to produce solar fuels or chemicals using sunlight. In particular, nanostructures featuring localized surface plasmon resonance (LSPR) hold great promise as photo-thermal catalysts given their ability to convert light into heat. In this regard, traditional plasmonic materials include gold (Au) or silver (Ag), but in the last years, transition metal nitrides have been proposed as a cost-efficient alternative. Herein, we demonstrate that titanium nitride (TiN) tubes derived from the nitridation of TiO₂ precursor display excellent light absorption properties thanks to their intense LSPR band in the visible–IR regions. Upon deposition of Ru nanoparticles (NPs), Ru-TiN tubes exhibit high activity towards the photo-thermal CO₂ reduction reaction, achieving remarkable methane (CH₄) production rates up to 1200 mmol g⁻¹ h⁻¹. Mechanistic studies suggest that the reaction pathway is dominated by thermal effects thanks to the effective light-to-heat conversion of Ru-TiN tubes. This work will serve as a basis for future research on new plasmonic structures for photo-thermal applications in catalysis.     

大面积多元化表面等离激元金纳米粒子结构的制备

具有显著表面等离激元共振效应的贵金属纳米粒子因其独特的光电学性质在许多领域表现出了潜在的应用价值. 结合纳米压印技术与自组装技术发展了一种高效的多元化纳米粒子结构的制备方法, 并制备了一种由不同尺寸金纳米粒子构成的周期性表面等离激元纳米粒子结构. 实验结果证明此种方法在大批量制备和结构多元化的控制方面具有独特的优势. 利用不同的表面等离激元纳米粒子结构对不同荧光分子增强效果的差异, 设计了2种具有明显明暗差异的荧光条码, 展示了多重的荧光增强响应.     

Hot‐Electron‐Transfer Enhancement for the Efficient Energy Conversion of Visible Light

Great strides have been made in enhancing solar energy conversion by utilizing plasmonic nanostructures in semiconductors. However, current generation with plasmonic nanostructures is still somewhat inefficient owing to the ultrafast decay of plasmon‐induced hot electrons. It is now shown that the ultrafast decay of hot electrons across Au nanoparticles can be significantly reduced by strong coupling with CdS quantum dots and by a Schottky junction with perovskite SrTiO₃ nanoparticles. The designed plasmonic nanostructure with three distinct components enables a hot‐electron‐assisted energy cascade for electron transfer, CdS→Au→SrTiO₃, as demonstrated by steady‐state and time‐resolved photoluminescence spectroscopy. Consequently, hot‐electron transfer enabled the efficient production of H₂ from water as well as significant electron harvesting under irradiation with visible light of various wavelengths. These findings provide a new approach for overcoming the low efficiency that is typically associated with plasmonic nanostructures.     

Plasmonic biosensing based on non-noble-metal materials

This review focuses on the research progress of non-noble-metal materials with nanostructures for plasmonic biosensing. Firstly, the physical and sensing principles of localized surface plasmon resonance (LSPR) sensors are briefly introduced; then non-noble-metal materials, such as copper, aluminum, semiconductor, graphene and other materials, for plasmonic sensing are categorized and presented. Finally, a rational discussion about the future prospective of novel materials for plasmonic sensing is given.     

Surface-enhanced Raman spectroscopy toward application in plasmonic photocatalysis on metal nanostructures

Among photothermal, photovoltaic and photochemical techniques, photochemistry is superior in energy storage and transportation by converting photons into chemical fuels. Recently plasmonic photocatalysis, based on localized surface plasmon resonance (LSPR) generated from noble metal nanostructures, has attracted much attention. It promotes photochemical reaction efficiency by optimizing the solar spectrum absorption and the surface reaction kinetics. The deeper understanding is in urgent need for the development of novel plasmonic photocatalysts. Surface-enhanced Raman spectroscopy (SERS), which is also originated from the LSPR effect, provides an excellent opportunity to probe and monitor plasmonic photoreactions in situ and in real-time, with a very high surface sensitivity and energy resolution. Here, fundamentals of plasmonic photocatalysis and SERS are first presented based on their connections to the LSPR effect. Following by a validity analysis, latest studies of SERS applied for the plasmon mediated photochemical reaction are reviewed, focusing on the reaction kinetics and mechanism exploration. Finally, limitations of the present study, as well as the future research directions, are briefly analyzed and discussed.     

Plasmonic heterogeneous catalysis for organic transformations

Plasmonic catalysis has been recognised as a promising alternative to many conventional thermal catalytic processes in organic synthesis. In addition to their high activity in fine chemical synthesis, plasmonic photocatalysts are also able to maintain control of selectivity under mild conditions by utilising visible-light as an energy source. This review provides an overview of the recent advances in organic transformations with plasmonic metal nanostructures, including selective reduction, selective oxidation, cross-coupling and addition reactions. We also summarize the photocatalysts and catalytic mechanisms involving surface plasmon resonance. Finally, control of reaction pathway and strategies for tailoring product selectivity in fine chemical synthesis are discussed.     

Metallic Heterostructures for Plasmon-Enhanced Electrocatalysis

Metallic heterogeneous nanostructures with plasmonic functionality have attracted great attention in the field of plasmon-enhanced electrocatalysis, where surface plasmons produced under light excitation could facilitate the overall electrocatalytic performances. Owing to their controllability, multifunctionality, and complexity, heterogeneous metallic nanostructures take advantages of the properties from individual components and synergistic effects from adjacent components, thus may achieve remarkable electrocatalytic performances. This review highlights the state-of-the-art progress of the application of metallic heterostructures for plasmon-enhanced electrocatalysis. First, a brief introduction to plasmonic heterogeneous nanostructures is demonstrated. Then, fundamental principles of localized surface plasmon resonance and the underlying mechanisms of plasmonic heterogeneous nanostructures in catalysis are discussed. This is followed by a discussion of recent advances of plasmonic heterogeneous nanostructures in plasmon-enhanced electrocatalysis, in which the enhanced activity, selectivity, and stability are particularly emphasized. Finally, an outlook of remaining challenges and future opportunities for plasmonic heterogeneous nanomaterials and plasmon-related electrocatalysis is presented.     

Coupling between molecular and plasmonic resonances in freestanding dye-gold nanorod hybrid nanostructures

Hybrid nanostructures of organic dyes and inorganic gold nanorods are constructed using the layer-by-layer assembly method via electrostatic interactions. Strong coupling is observed between the molecular resonance of dyes and the plasmonic resonance of gold nanorods when their spectra overlap strongly. The coupling strength is tuned by choosing gold nanorods with longitudinal plasmon wavelengths varying from 570 to 870 nm. The resonance coupling-induced plasmon shift is found to be strongly dependent on the dye concentration and the spacing between the dye and nanorod. Moreover, the resonance coupling can be switched off by laser illumination to decompose adsorbed dyes. We believe this is the first time that the coupling between molecular and plasmonic resonances is observed for freestanding hybrid nanostructures constructed out of dyes and colloidal gold nanorods. These results will be helpful in understanding the fundamental interactions between molecular and plasmonic resonances and useful for the design of resonance coupling-based chemical and biological sensors.     

Strong Light‐Molecule Coupling on Plasmonic Arrays of Different Symmetry

The strong coupling of porphyrin J‐aggregates to plasmonic nanostructures of different symmetry is investigated. The nanostructures of higher symmetry show the strongest interaction with the molecular layer, suggesting that surface plasmon mode degeneracy plays an important role in the coupling efficiency. At high coupling strengths a new, weakly dispersive mode appears which has recently been predicted theoretically to be due to long‐range energy transfer between molecules mediated by surface plasmons. These findings point to new ways for optimizing strong coupling and thereby realize its full potential for molecular and material science.     

Plasmonics for pulsed-laser cell nanosurgery: Fundamentals and applications

This review describes the fundamental aspects of pulsed laser interaction with plasmonic nanostructures, and its applications to cell nanosurgery, including the destruction, modification or manipulation of molecular, sub-cellular and cellular structures. The review assumes no prior knowledge of the field of plasmonics and begins with a short review of the basic theory of plasmon excitation and optical properties of nanoscale metallic structures. Fundamentals of short and ultrashort laser pulse interaction with plasmonic nanostructures in a water environment are then discussed. Special emphasis is put on the consequences of the irradiation on the surrounding environment of the nanostructure, including heating, low-density plasma generation, pressure wave release and formation of vapor bubbles. The paper is concluded with a review of different applications of pulsed-laser interaction with plasmonic nanostructures for cell nanosurgery, including photothermal therapy, plasmonic enhanced cell transfection, molecular surgery and drug delivery.     

Nanoplasmonic zirconium nitride photocatalyst for direct overall water splitting

The ability of plasmonic nanostructures to efficiently harvest light energy and generate energetic hot carriers makes them promising materials for utilization in photocatalytic water spitting.Apart from the traditional Au and Ag based plasmonic photocatalysts,more recently the noble-metal-free alternative plasmonic materials have attracted ever-increasing interest.Here we report the first use of plasmonic zirconium nitride（ZrN） nanoparticles as a promising photocatalyst for water splitting.Highl...     

Surfactant‐Free Nonaqueous Synthesis of Plasmonic Molybdenum Oxide Nanosheets with Enhanced Catalytic Activity for Hydrogen Generation from Ammonia Borane under Visible Light

Plasmonic materials have drawn emerging interest, especially in nontraditional semiconductor nanostructures with earth‐abundant elements and low resistive loss. However, the actualization of highly efficient catalysis in plasmonic semiconductor nanostructures is still a challenge, owing to the presence of surface‐capping agents in their synthetic procedures. To fulfill this, a facile non‐aqueous procedure was employed to prepare well‐defined molybdenum oxide nanosheets in the absence of surfactants. The obtained MoO_3‐x nanosheets display intense absorption in a wide range attributed to the localized surface plasmon resonances, which can be tuned from the visible to the near‐infrared region. Herein, we demonstrate that such plasmonic semiconductor nanostructures could be used as highly efficient catalysts that dramatically enhance the hydrogen‐generation activity of ammonia borane under visible light irradiation.