Plasmonic Catalysis Research Articles

Nanoscale structural characterization of plasmon-driven reactions

Abstract Illumination of noble metal nanostructures by electromagnetic radiation induces coherent oscillations of conductive electrons on their surfaces. These coherent oscillations of electrons, also known as localized surface plasmon resonances (LSPR), are the underlying physical cause of the electromagnetic enhancement of Raman scattering from analytes located in a close proximity to the metal surface. This physical phenomenon is broadly known as surface-enhanced Raman scattering (SERS). LSPR can decay via direct interband, phonon-assisted intraband, and geometry-assisted transitions forming hot carriers, highly energetic species that are responsible for a large variety of chemical transformations. This review critically discusses the most recent progress in mechanistic elucidation of hot carrier-driven chemistry and catalytic processes at the nanoscale. The review provides a brief description of tip-enhanced Raman spectroscopy (TERS), modern analytical technique that possesses single-molecule sensitivity and angstrom spatial resolution, showing the advantage of this technique for spatiotemporal characterization of plasmon-driven reactions. The review also discusses experimental and theoretical findings that reported novel plasmon-driven reactivity which can be used to catalyze redox, coupling, elimination and scissoring reactions. Lastly, the review discusses the impact of the most recently reported findings on both plasmonic catalysis and TERS imaging.

Plasmonic photothermal catalysis for solar-to-fuel conversion: current status and prospects.

Solar-to-fuel conversion through photocatalytic processes is regarded as promising technology with the potential to reduce reliance on dwindling reserves of fossil fuels and to support the sustainable development of our society. However, conventional semiconductor-based photocatalytic systems suffer from unsatisfactory reaction efficiencies due to limited light harvesting abilities. Recent pioneering work from several groups, including ours, has demonstrated that visible and infrared light can be utilized by plasmonic catalysts not only to induce local heating but also to generate energetic hot carriers for initiating surface catalytic reactions and/or modulating the reaction pathways, resulting in synergistically promoted solar-to-fuel conversion efficiencies. In this perspective, we focus primarily on plasmon-mediated catalysis for thermodynamically uphill reactions converting CO2 and/or H2O into value-added products. We first introduce two types of mechanism and their applications by which reactions on plasmonic nanostructures can be initiated: either by photo-induced hot carriers (plasmonic photocatalysis) or by light-excited phonons (photothermal catalysis). Then, we emphasize examples where the hot carriers and phonon modes act in concert to contribute to the reaction (plasmonic photothermal catalysis), with special attention given to the design concepts and reaction mechanisms of the catalysts. We discuss challenges and future opportunities relating to plasmonic photothermal processes, aiming to promote an understanding of underlying mechanisms and provide guidelines for the rational design and construction of plasmonic catalysts for highly efficient solar-to-fuel conversion.

Coupling plasmonic catalysis and nanocrystal growth through cyclic regeneration of NADH.

In a typical colloidal synthesis, the molecules of the reducing agent are irreversibly oxidized during nanocrystal growth. Such a scenario is of questionable sustainability when confronted with naturally occurring processes in which reducing agent molecules are cyclically regenerated. Here we show that cofactor molecules once consumed in the nucleation and growth of metallic nanocrystals can be photoregenerated using metallic nanocrystals as photocatalysts and reused in the subsequent nucleation process. Cyclic regeneration of cofactor molecules opens up the possibilities for the sustainable synthesis of inorganic nanoparticles.

Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters.

Light-driven plasmonic enhancement of chemical reactions on metal catalysts is a promising strategy to achieve highly selective and efficient chemical transformations. The study of plasmonic catalyst materials has traditionally focused on late transition metals such as Au, Ag, and Cu. In recent years, there has been increasing interest in the plasmonic properties of a set of earth-abundant elements such as Mg, which exhibit interesting hydrogenation chemistry with potential applications in hydrogen storage. This work explores the optical, electronic, and catalytic properties of a set of metallic Mg nanoclusters with up to 2057 atoms using time-dependent density functional tight-binding and density functional theory calculations. Our results show that Mg nanoclusters are able to produce highly energetic hot electrons with energies of up to 4 eV. By electronic structure analysis, we find that these hot electrons energetically align with electronic states of physisorbed molecular hydrogen, occupation of which by hot electrons can promote the hydrogen dissociation reaction. We also find that the reverse reaction, hydrogen evolution on metallic Mg, can potentially be promoted by hot electrons, but following a different mechanism. Thus, from a theoretical perspective, Mg nanoclusters display very promising behaviour for their use in light promoted storage and release of hydrogen.

Challenges in Plasmonic Catalysis.

The use of nanoplasmonics to control light and heat close to the thermodynamic limit enables exciting opportunities in the field of plasmonic catalysis. The decay of plasmonic excitations creates highly nonequilibrium distributions of hot carriers that can initiate or catalyze reactions through both thermal and nonthermal pathways. In this Perspective, we present the current understanding in the field of plasmonic catalysis, capturing vibrant debates in the literature, and discuss future avenues of exploration to overcome critical bottlenecks. Our Perspective spans first-principles theory and computation of correlated and far-from-equilibrium light-matter interactions, synthesis of new nanoplasmonic hybrids, and new steady-state and ultrafast spectroscopic probes of interactions in plasmonic catalysis, recognizing the key contributions of each discipline in realizing the promise of plasmonic catalysis. We conclude with our vision for fundamental and technological advances in the field of plasmon-driven chemical reactions in the coming years.

Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control.

Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C-N bond and forming a new C-C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. This work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.

Growth of Nanostructured Silver Flowers by Metal-Mediated Catalysis for Surface-Enhanced Raman Spectroscopy Application.

Metallic flowers with nanoscale surface roughness can provide a platform for highly sensitive and reproductive surface-enhanced Raman spectroscopy (SERS). Here, we present a method to grow a nanostructured silver flower (NSF) at the apex of a plasmonic tip based on metal-mediated catalysis, where the NSF was rapidly generated in no more than 1 min. The NSF was used as the SERS substrate under linear polarization beam (LPB) excitation to achieve a 10–9 M detection sensitivity for the malachite green analyte. The reproducibility for SERS is examined to have been guaranteed by comparing Raman intensity enhanced by different NSFs. Compared with the LPB, the azimuthal vector beam (AVB) excitation can further improve the SERS activity of the NSF, which is consistent with the simulation result that the gap mode can be effectively generated between two adjacent Ag nanoparticles (NPs) and between the NPs and the Ag pyramids on the surface of the NSF under AVB illumination. This work makes it promising for plasmonic tip-mediated catalysis to be applied in nanofabrication, the products of which can be further exploited in nanostructure-based ultrasensitive detection.

Collective photothermal effect of Al2O3‐supported spheroidal plasmonic Ru nanoparticle catalysts in the sunlight‐powered Sabatier reaction

AbstractPlasmon catalysis is an interesting technology concept for powering chemical processes with light. Here, we report the use of various Al2O3‐supported Ru spheroidal nanoparticles as catalyst for the low‐temperature conversion of CO2 and H2 to CH4 (Sabatier reaction), using sunlight as energy source. At high loadings of Ru spheroidal nanoparticles (5.9 % w/w), we observe a sharp increase in the rate of the sunlight powered reaction when compared to the reaction in dark at the same catalyst bed temperature. Based on our results we exclude plasmon coupling as cause, and attribute the rate enhancement to collective photothermal heating of the Al2O3‐supported Ru nanoparticles.

Noble metallic nanoparticles from waste Nypa fruticans fruit husk: Biosynthesis, characterization, antibacterial activity and recyclable catalysis

Biogenic synthesis of noble metal nanoparticles is particularly interested due to the effective applications for plasmonic catalysis and bioactivity. In this work, aqueous extract of waste Nypa fruticans (NF) fruit husk was utilized to synthesize silver nanoparticles (NF-AgNPs) and gold nanoparticles (NF-AuNPs). The effected parameters on the green reduction of metallic nanoparticles (MNPs) were investigated. Under optimum conditions of concentration, temperature and time, the biosynthesized NF-AgNPs and NF-AuNPs showed spherical nanoparticles with average size of 10–15 nm and 15–20 nm, respectively. The presence of AgCl in NF-AgNPs has been demonstrated by X-ray diffraction analysis. The elemental components of all samples confirmed the presence of anions and cations come from the aqueous extract. The biosynthesized nanoparticles were evaluated bacterial activity against three bacterial strains. NF-AgNPs exhibited selective antibacterial activity against Bacillus cereus but no activity against Staphylococcus aureus and Salmonella typhimurium at all tested concentrations. The recyclable catalysis activity of the biosynthesized nanoparticles was evaluated for the reduction of nitrophenols in the presence of sodium borohydride which possessed good catalytic performance in six running numbers. Additionally, AgCl played role as a source supplying AgNPs has been demonstrated in catalytic reduction of p-nitrophenol. For study of catalytic kinetic, NF-AgNPs possessed higher rate constant in comparison with NF-AuNPs whereas TOF values of NF-AuNPs was determined to be higher than those of NF-AgNPs.

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination.

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular transformations. This opens possibilities for the use of visible or near-IR light as a sustainable input to drive and control reactions when plasmonic nanoparticles supporting LSPR excitation in these ranges are employed as catalysts. Unfortunately, this is not the case for several catalytic metals such as palladium (Pd). One strategy to overcome this limitation is to employ bimetallic NPs containing plasmonic and catalytic metals. In this case, the LSPR excitation in the plasmonic metal can contribute to accelerate and control transformations driven by the catalytic component. The method reported herein focuses on the synthesis of bimetallic silver-palladium (Ag-Pd) NPs supported on ZrO2 (Ag-Pd/ZrO2) that acts as a plasmonic-catalytic system. The NPs were prepared by co-impregnation of corresponding metal precursors on the ZrO2 support followed by simultaneous reduction leading to the formation of bimetallic NPs directly on the ZrO2 support. The Ag-Pd/ZrO2 NPs were then used as plasmonic catalysts for the reduction of nitrobenzene under 425 nm illumination by LED lamps. Using gas chromatography (GC), the conversion and selectivity of the reduction reaction under the dark and light irradiation conditions can be monitored, demonstrating the enhanced catalytic performance and control over selectivity under LSPR excitation after alloying non-plasmonic Pd with plasmonic metal Ag. This technique can be adapted to a wide range of molecular transformations and NPs compositions, making it useful for the characterization of the plasmonic catalytic activity of different types of catalysis in terms of conversion and selectivity.

Light-Induced Voltages in Catalysis by Plasmonic Nanostructures.

ConspectusPlasmonic nanostructures have garnered widescale scientific interest because of their strong light-matter interactions and the tunability of their absorption across the solar spectrum. At the heart of their superlative interaction with light is the resonant excitation of a collective oscillation of electrons in the nanostructure by the incident electromagnetic field. These resonant oscillations are known as localized surface plasmon resonances (LSPRs). In recent years, the community has uncovered intriguing photochemical attributes of noble metal nanostructures arising from their LSPRs. Chemical reactions that are otherwise unfavorable or sluggish in the dark are induced on the nanostructure surface upon photoexcitation of LSPRs. This phenomenon has led to the birth of plasmonic catalysis. The rates of a variety of kinetically challenging reactions are enhanced by plasmon-excited nanostructures. While the potential utility for solar energy harvesting and chemical production is clear, there is a natural curiosity about the precise origin(s) of plasmonic catalysis. One explanation is that the reactions are facilitated by the action of the intensely concentrated and confined electric fields generated on the nanostructure upon LSPR excitation. Another mechanism of activation involves hot carriers transiently produced in the metal nanostructure by damping of LSPRs.In this Account, we visit a phenomenon that has received less attention but has a key role to play in plasmonic catalysis and chemistry. Under common chemical scenarios, plasmonic excitation induces a potential or a voltage on a nanoparticle. This photopotential modifies the energetics of a chemical reaction on noble metal nanoparticles. In a range of cases studied by our laboratory and others, light-induced potentials underlie the plasmonic enhancement of reaction kinetics. The photopotential model does not replace other known mechanisms, but it complements them. There are multiple ways in which an electrostatic photopotential is produced by LSPR excitation, such as optical rectification, but one that is most relevant in chemical media is asymmetric charge transfer to solution-phase acceptors. Electrons and holes produced in a nanostructure by damping of LSPRs are not removed at the same rate. As a result, the slower carrier accumulates on the nanostructure, and a steady-state charge is built up on the nanostructure, leading to a photopotential. Potentials of up to a few hundred millivolts have been measured by our laboratory and others. A photocharged nanoparticle is a source of carriers of a higher potential than an uncharged one. As a result, redox chemical reactions on noble metal nanoparticles exhibit lower activation barriers under photoexcitation. In electrochemical reactions on noble metal nanoparticles, the photopotential supplements the applied potential. In a diverse set of reactions, the photopotential model explains the photoenhancement of rates as well as the trends as a function of light intensity and photon energy. With further gains, light-induced potentials may be used as a knob for controlling the activities and selectivities of noble metal nanoparticle catalysts.

Elucidation of Photocatalytic Properties of Gold–Platinum Bimetallic Nanoplates Using Tip-Enhanced Raman Spectroscopy

Plasmonic catalysis is based on a unique property of noble metal nanostructures to harvest electromagnetic radiation converting it into hot carriers. These high energy species can catalyze chemical reactions in molecules located in the vicinity to surfaces of the plasmonic nanostructures. However, traditional plasmonic metals such as gold (Au) are useful only for a limited number of chemical reactions. The spectrum of chemical reactions can be broadened up by coupling plasmonic and catalytic metals, such as platinum (Pt), in one nanostructure. In this study, we use tip-enhanced Raman spectroscopy (TERS) to probe photocatalytic properties of gold–platinum nanoplates (Au@PtNPs). We found that Au@PtNPs highly efficiently proto-reduced 4-nitrobenzenethiol (4-NBT) to p,p′-dimercaptoazobisbenzene (DMAB) with the yield similar to the one observed for gold nanoplates (AuNPs). These Au@PtNPs could be used to proto-oxidize 4-aminothiophenol (4-ATP) first to 4-NBT and then 4-NBT to DMAB, whereas photo-oxidation of 4-ATP on the surface of AuNPs directly proceeds to DMAB.

The Efficient Ionization Reaction of DTBA Achieved by Surface Plasmon Catalysis Effect

4,4’-Dithiobisbenzoic acid (DTBA) is equivalent to two 4-mercaptobenzoic acid (pMBA) molecules connected together after losing H+, and this bimolecular mechanism of DTBA efficiently promotes the ionization reaction. Under the irradiation of laser light, DTBA molecules are broken to form bimolecules similar to pMBA, and this kind of bimolecular coupling greatly increases the probability of binding with Ag NPs. Also, this molecule has the carboxylic acid group, which leads to a certain sensitivity to pH. In this article, through the comparison of DTBA and pMBA parallel experiments, it is clear that DTBA has better Raman activity, higher reaction efficiency, and more stable reaction than pMBA. The occurrence of this highly efficient ionization reaction under the monitoring of surface-enhanced Raman spectroscopy (SERS) provides a certain value for the progress of further related reactions, and it also has a wide range of applications in pH sensors and intracellular pH monitoring.

Gold nanotriangles with magnetite satellites

This work describes the synthesis of hybrid particles of gold nanotriangles (AuNTs) with magnetite nanoparticles (MNPs) by using 1-mercaptopropyl-3-trimethoxysilan (MPTMS) and L-cysteine as linker molecules. Due to the combination of superparamagnetic properties of MNPs with optical properties of the AuNTs, nanoplatelet-satellite hybrid nanostructures with combined features become available. By using MPTMS with silan groups as linker molecule a magnetic “cloud” with embedded AuNTs can be separated. In presence of L-cysteine as linker molecule at pH > pHiso a more unordered aggregate structure of MNPs is obtained due to the dimerization of the L-cysteine. At pH < pHiso water soluble positively charged AuNTs with satellite MNPs can be synthesized. The time-dependent loading with MNP satellites under release of the extinction and magnetization offer a hybrid material, which is of special relevance for biomedical applications and plasmonic catalysis.

Kinetics of molecular decomposition under irradiation of gold nanoparticles with nanosecond laser pulses-A 5-Bromouracil case study.

Laser illuminated gold nanoparticles (AuNPs) efficiently absorb light and heat up the surrounding medium, leading to versatile applications ranging from plasmonic catalysis to cancer photothermal therapy. Therefore, an in-depth understanding of the thermal, optical, and electron induced reaction pathways is required. Here, the electrophilic DNA nucleobase analog 5-Bromouracil (BrU) has been used as a model compound to study its decomposition in the vicinity of AuNPs illuminated with intense ns laser pulses under various conditions. The plasmonic response of the AuNPs and the concentration of BrU and resulting photoproducts have been tracked by ultraviolet and visible (UV-Vis) spectroscopy as a function of the irradiation time. A kinetic model has been developed to determine the reaction rates of two parallel fragmentation pathways of BrU, and their dependency on laser fluence and adsorption on the AuNP have been evaluated. In addition, the size and the electric field enhancement of the decomposed AuNPs have been determined by atomic force microscopy and finite domain time difference calculations, respectively. A minor influence of the direct photoreaction and a strong effect of the heating of the AuNPs have been revealed. However, due to the size reduction of the irradiated AuNPs, a trade-off between laser fluence and plasmonic response of the AuNPs has been observed. Hence, the decomposition of the AuNPs might be limiting the achievable temperatures under irradiation with several laser pulses. These findings need to be considered for an efficient design of catalytic plasmonic systems.

Surface-Enhanced Hyper Raman Spectra of Aromatic Thiols on Gold and Silver Nanoparticles.

We report the two-photon excited nonresonant surface-enhanced hyper Raman scattering (SEHRS) spectra of six aromatic thiol molecules during their interaction with gold and silver nanostructures. SEHRS spectra were obtained from thiophenol, benzyl mercaptan, and phenylethyl mercaptan and from the three isomers 2-aminothiophenol (2-ATP), 3-aminothiophenol (3-ATP), and 4-aminothiophenol (4-ATP). All SEHRS spectra were excited off-resonance at a wavelength of 1064 nm and compared to surface-enhanced Raman scattering (SERS) spectra excited at 785 nm or at 633 nm. The SEHRS spectra show a different interaction of thiophenol, benzyl mercaptan, and phenylethyl mercaptan with silver and gold nanostructures. Density functional theory calculations were used to support band assignments, in particular, for the unknown SERS spectrum of 3-ATP, and identify a band of phenylethyl mercaptan as a vibrational mode unique to the SEHRS spectrum and very weak in the Raman and infrared spectra. 2-ATP, 3-ATP, and 4-ATP show a different interaction with gold nanostructures that was found to depend on pH. Bands in the SEHRS spectrum of 2-ATP could be assigned to 2,2′-dimercaptoazobenzene, suggested to be obtained in a plasmon-assisted reaction that occurred during the SEHRS experiment. The results provide the basis for a better characterization of organic thiols at surfaces in a variety of fields, including surface functionalization and plasmonic catalysis.

Silver thin film deposited 3-dimensional gold nanorod arrays for plasmonic catalysis

Plasmonic metal nanoparticles are of great importance in heterogeneous catalysis applications including partial oxidations, dehydrogenations, and hydrocarbon reforming. Although utilization of such nanoparticulate metals seems to be a simple and cheap approach for catalysis, their low surface area, un-controlled aggregation, and limited recovery and recycling abilities prevent their further applications. Herein, to overcome these limitations, vertically aligned, highly ordered, and unidirectional 3-dimensional (3D) gold nanorod (AuNR) arrays were fabricated through an oblique angle vapor deposition method. The plasmonic features and catalytic efficiencies of 3D AuNR arrays were further improved by combining them with a thin layer of silver having varying thicknesses. The catalytic activity of fabricated samples was evaluated by the reduction of 4-nitrophenol to 4-aminophenol with NaBH4 in the absence and presence of laser illumination with different wavelengths. All the results indicate that the current Ag@AuNR substrates are expected to have a broad impact in a range of fields including plasmonic catalysis, sensing, and many others.

Fast transformation of a rare-earth doped luminescent sub-microcrystal via plasmonic nanoislands

Efficient and fast micro-crystal transformation by plasmonic catalysis of Au nanoislands.

Decoding the kinetic limitations of plasmon catalysis: the case of 4-nitrothiophenol dimerization.

Plasmon-mediated chemistry presents an intriguing new approach to photocatalysis. However, the reaction enhancement mechanism is not well understood. In particular, the relative importance of plasmon-generated hot charges and photoheating is strongly debated. In this article, we evaluate the influence of microscopic photoheating on the kinetics of a model plasmon-catalyzed reaction: the light-induced 4-nitrothiophenol (4NTP) to 4,4'-dimercaptoazobenzene (DMAB) dimerization. Direct measurement of the reaction temperature by nanoparticle Raman-thermometry demonstrated that the thermal effect plays a dominant role in the kinetic limitations of this multistep reaction. At the same time, no reaction is possible by dark heating to the same temperature. This shows that plasmon nanoparticles have the unique ability to enhance several steps of complex tandem reactions simultaneously. These results provide insight into the role of hot electron and thermal effects in plasmonic catalysis of complex organic reactions, which is highly important for the ongoing development of plasmon based photosynthesis.