Nonplasmonic Metals Research Articles

Near Field Scattering Optical Model-Based Catalyst Design for Artificial Photoredox Transformation

The sun offers a clean and renewable energy cornucopia, whereas how to utilize this inexhaustible yet decentralized energy with the assistance of appropriate media is an enduring topic. Plasmonic metal-based nanostructures (mainly Au and Ag) represent a class of fascinating materials for solar energy conversion due to their exclusive surface plasmon resonance (SPR)-enabled light-harvesting capability. In contrast to these plasmonic metals with characteristic SPR peaks, modulating the optical absorption peaks of nonplasmonic metals (e.g., small Pt nanoparticles) in the visible region but without size alteration is a grand challenge. Until recently, we demonstrated a near field scattering (NFS) optical model to manipulate the absorption peaks of Pt nanoparticles by adjusting their dielectric environment, sowing the seeds for tuning the optical absorption property of other metal nanoparticles and even semiconductor quantum dots. It is the purpose of the present Perspective to retrospect the history of NFS optical model and guide the function-oriented design of NFS-based nanostructures for artificial photoredox transformation.

Recent advances on photo-thermo-catalysis for carbon dioxide methanation

The carbon dioxide (CO2) hydrogenation into methane (CH4, Sabatier reaction) has intrigued much research attention considering the role of CH4 in rendering energy for daily life. Photo-thermo-catalysis (PTC) of CO2 methanation integrates both photochemical and thermochemical contributions to drive CH4 generation effectively and selectively. This review critically surveys recent discoveries in PTC-CO2 methanation. After introducing the basics of CO2 methanation, the mechanisms of PTC-CO2 methanation related to electron transfer (non-thermal effect) and photothermal heating are presented. Next, the factors regarding metals, shapes, metal–support interactions and defects are discussed. Moreover, we highlight the emerging catalysts of PTC-CO2 methanation, including plasmonic and non-plasmonic metals, metal oxide semiconductors, metal-organic frameworks, and metal carbides. This review concludes with current challenges and future perspectives in paving the way toward the industrial application of PTC-CO2 methanation.

Pt nanoparticles enhanced TiO2 on ultra-violet photo-detection: Hot-electron injection effect over near-field enhancement

Non-plasmonic metal has been attracting considerable research attentions in direct generation of photocurrent owing to their unique electronic band structure. In this paper, Pt nanoparticles (NPs) are fabricated by solid-state dewetting (SSD) with controllable dimensions. By sol–gel method, TiO2 layers are deposited on top of Pt NPs and the dielectric effect on Pt NPs was investigated, based on optical measurements as well as the absorption cross-sections and near-field distribution that calculated via finite difference time domain method. The photoelectric properties of TiO2/Pt NPs layers are characterized based on the fabrication of photo-FETs. The photo-electronic performance of TiO2 are significantly improved by addition of Pt NPs, however, the improvement under xenon light excitation is much weaker than UV light. The results reveal the vital role of hot-electron injection over near-field enhancement, which can be a reference for future design of high-performance plasmonic devices.

Photoacoustic laser streaming with non-plasmonic metal ion implantation in transparent substrates.

Photoacoustic laser streaming provides a versatile technique to manipulate liquids and their suspended objects with light. However, only gold was used in the initial demonstrations. In this work, we first demonstrate that laser streaming can be achieved with common non-plasmonic metals such as Fe and W by their ion implantations in transparent substrates. We then investigate the effects of ion dose, substrate material and thickness on the strength and duration of streaming. Finally, we vary laser pulse width, repetition rate and power to understand the observed threshold power for laser streaming. It is found that substrate thickness has a negligible effect on laser streaming down to 0.1 mm, glass and quartz produce much stronger streaming than sapphire because of their smaller thermal conductivity, while quartz exhibits the longest durability than glass and sapphire under the same laser intensity. Compared with Au, Fe and W with higher melting points show a longer lifetime although they require a higher laser intensity to achieve a similar speed of streaming. To generate a continuous laser streaming, the laser must have a minimum pulse repetition rate of 10 Hz and meet the minimum pulse width and energy to generate a transient vapor layer. This vapor layer enhances the generation of ultrasound waves, which are required for observable fluid jets. Principles of laser streaming and temperature simulation are used to explain these observations, and our study paves the way for further materials engineering and device design for strong and durable laser streaming.

Sunlight-Operated TiO2-Based Photocatalysts.

Photo-catalysis is a research field with broad applications in terms of potential technological applications related to energy production and managing, environmental protection, and chemical synthesis fields. A global goal, common to all of these fields, is to generate photo-catalytic materials able to use a renewable energy source such as the sun. As most active photocatalysts such as titanium oxides are essentially UV absorbers, they need to be upgraded in order to achieve the fruitful use of the whole solar spectrum, from UV to infrared wavelengths. A lot of different strategies have been pursued to reach this goal. Here, we selected representative examples of the most successful ones. We mainly highlighted doping and composite systems as those with higher potential in this quest. For each of these two approaches, we highlight the different possibilities explored in the literature. For doping of the main photocatalysts, we consider the use of metal and non-metals oriented to modify the band gap energy as well as to create specific localized electronic states. We also described selected cases of using up-conversion doping cations. For composite systems, we described the use of binary and ternary systems. In addition to a main photo-catalyst, these systems contain low band gap, up-conversion or plasmonic semiconductors, plasmonic and non-plasmonic metals and polymers.

Photo–thermo Catalytic Oxidation over a TiO2‐WO3‐Supported Platinum Catalyst

AbstractPhoto–thermo catalysis, which integrates photocatalysis on semiconductors with thermocatalysis on supported nonplasmonic metals, has emerged as an attractive approach to improve catalytic performance. However, an understanding of the mechanisms in operation is missing from both the thermo‐ and photocatalytic perspectives. Deep insights into photo–thermo catalysis are achieved via the catalytic oxidation of propane (C3H8) over a Pt/TiO2‐WO3 catalyst that severely suffers from oxygen poisoning at high O2/C3H8 ratios. After introducing UV/Vis light, the reaction temperature required to achieve 70 % conversion of C3H8 lowers to a record‐breaking 90 °C from 324 °C and the apparent activation energy drops from 130 kJ mol−1 to 11 kJ mol−1. Furthermore, the reaction order of O2 is −1.4 in dark but reverses to 0.1 under light, thereby suppressing oxygen poisoning of the Pt catalyst. An underlying mechanism is proposed based on direct evidence of the in‐situ‐captured reaction intermediates.

Photo-thermo Catalytic Oxidation over a TiO2 -WO3 -Supported Platinum Catalyst.

Photo-thermo catalysis, which integrates photocatalysis on semiconductors with thermocatalysis on supported nonplasmonic metals, has emerged as an attractive approach to improve catalytic performance. However, an understanding of the mechanisms in operation is missing from both the thermo- and photocatalytic perspectives. Deep insights into photo-thermo catalysis are achieved via the catalytic oxidation of propane (C3 H8 ) over a Pt/TiO2 -WO3 catalyst that severely suffers from oxygen poisoning at high O2 /C3 H8 ratios. After introducing UV/Vis light, the reaction temperature required to achieve 70 % conversion of C3 H8 lowers to a record-breaking 90 °C from 324 °C and the apparent activation energy drops from 130 kJ mol-1 to 11 kJ mol-1 . Furthermore, the reaction order of O2 is -1.4 in dark but reverses to 0.1 under light, thereby suppressing oxygen poisoning of the Pt catalyst. An underlying mechanism is proposed based on direct evidence of the in-situ-captured reaction intermediates.

Photocatalysis Using Earth-Abundant Copper-Based Plasmonic and High-Dielectric Nanostructures to Produce High-Value Chemicals

Over the years plasmonic materials have received wide attention for their ability to convert solar into chemical energy. Plasmonic nanoparticles (NPs) exhibit strong electromagnetic-field (EMF) enhancement for the incident light because of the Localized Surface Plasmon Resonance (LSPR). This property has been shown to enhance the photocatalytic performance of nearby semiconductors in the composite, and hybrid photocatalysts build on plasmonic metal nanoparticle and semiconductor. In this presentation, we will focus on copper based hybrid plasmonic nanostructures and optically resonant high dielectric nanostructures for efficient conversion of solar into chemical energy. Our FDTD simulation results predict that the EMF enhancement observed over high dielectric NPs are 2-3 orders of magnitude higher than the plasmonic NPs. This new family of non-plasmonic metal oxide nanostructures is dielectric in nature with high refractive index (> 2). Our simulation results predict that the Mie resonance over these high-dielectric nanostructures can be tuned anywhere from UV-Vis to the near-IR region by controlling the geometry of the nanostructures. We will also show experimental results that validate the simulation results. We utilized size and shape-controlled synthesis techniques to design optically resonant nanostructures with tunable Mie resonance. The optoelectronic properties of these nanostructures are confirmed using a number of spectroscopic techniques. Also, we will show the visible-light enhanced photocatalytic performance of the high dielectric nanostructures for carbon-carbon (C-C) coupling reactions. The design rules developed for the optically resonant nanostructures in our study will potentially have a wide range of applications including the use of these nanostructures for solar-light driven photocatalysis and thin-film solar cell applications.

Design Principles for Directing Energy and Energetic Charge Flow in Multicomponent Plasmonic Nanostructures

The decay of localized surface plasmons supported by plasmonic metal nanoparticles results in the formation of energetic charge carriers within the nanoparticles. Once formed, these charge carriers can transfer to chemically attached materials where they can perform a function. The efficient extraction and utilization of these charge carriers in various applications hinges on the ability to design plasmonic nanostructures with highly localized charge carrier generation at specific locations in the nanostructure. Herein, we shed light on the physical mechanisms governing the flow of energy in resonantly excited multimetallic plasmonic nanoparticles. We demonstrate that coating plasmonic nanostructures with nonplasmonic metals can result in the preferential dissipation of energy (i.e., formation of charge carriers) in the nonplasmonic metal and that the extent of this dissipation depends heavily on the electronic structure of the constituent metals. We use experimental and modeling studies of various core–s...

Correlated Absorption and Scattering Spectroscopy of Individual Platinum-Decorated Gold Nanorods Reveals Strong Excitation Enhancement in the Nonplasmonic Metal.

Bimetallic nanocatalysts have the potential to surmount current limitations in industrial catalysis if their electronic and optical properties can be effectively controlled. However, improving the performance of bimetallic photocatalysts requires a functional understanding of how the intricacies of their morphology and composition dictate every element of their optical response. In this work, we examine Au and Pt-decorated Au nanorods on a single-particle level to ascertain how Pt influences the plasmon resonance of the bimetallic nanostructure. We correlated scattering, photoluminescence, and pure absorption of individual nanostructures separately to expose the impact of Pt on each component. We found that the scattering and absorption spectra of uncoated Au nanorods followed expected trends in peak intensity and shape and were accurately reproduced by finite difference time domain simulations. In contrast, the scattering and absorption spectra of single Pt-decorated Au nanorods exhibited red-shifted, broad features and large deviations in line shape from particle to particle. Simulations using an idealized geometry confirmed that Pt damps the plasmon resonance of individual Au nanorods and that spectral changes after Pt deposition were a consequence of coupling between Au and Pt in the hybrid nanostructure. Simulations also revealed that the Au nanorod acts as an antenna and enhances absorption in the Pt islands. Furthermore, comparing photoluminescence spectra from Au and Pt-decorated Au nanorods illustrated that emission was significantly reduced in the presence of Pt. The reduction in photoluminescence intensity indicates that Pt lowers the number of hot carriers in the Au nanorod available for radiative recombination through either direct production of hot carriers in Pt following enhanced absorption or charge transfer from Au to Pt. Overall, these results confirm that the Pt island morphology and distribution on the nanorod surface contribute to the optical response of individual hybrid nanostructures and that the damping observed in ensemble measurements originates not only from structural heterogeneity but also because of significant damping in single nanostructures.

Photon Energy Threshold in Direct Photocatalysis with Metal Nanoparticles: Key Evidence from the Action Spectrum of the Reaction.

By investigating the action spectra (the relationship between the irradiation wavelength and apparent quantum efficiency of reactions under constant irradiance) of a number of reactions catalyzed by nanoparticles including plasmonic metals, nonplasmonic metals, and their alloys at near-ambient temperatures, we found that a photon energy threshold exists in each photocatalytic reaction; only photons with sufficient energy (e.g., higher than the energy level of the lowest unoccupied molecular orbitals) can initiate the reactions. This energy alignment (and the photon energy threshold) is determined by various factors, including the wavelength and intensity of irradiation, molecule structure, reaction temperature, and so forth. Hence, distinct action spectra were observed in the same type of reaction catalyzed by the same catalyst due to a different substituent group, a slightly changed reaction temperature. These results indicate that photon-electron excitations, instead of the photothermal effect, play a dominant role in direct photocatalysis of metal nanoparticles for many reactions.

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna-Reactor Plasmonic Photocatalysis.

Efficient photocatalysis requires multifunctional materials that absorb photons and generate energetic charge carriers at catalytic active sites to facilitate a desired chemical reaction. Antenna-reactor complexes are an emerging multifunctional photocatalytic structure where the strong, localized near field of the plasmonic metal nanoparticle (e.g., Ag) is coupled to the catalytic properties of the nonplasmonic metal nanoparticle (e.g., Pt) to enable chemical transformations. With an eye toward sustainable solar driven photocatalysis, we investigate how the structure of antenna-reactor complexes governs their photocatalytic activity in the light-limited regime, where all photons need to be effectively utilized. By synthesizing core@shell/satellite (Ag@SiO2/Pt) antenna-reactor complexes with varying Ag nanoparticle diameters and performing photocatalytic CO oxidation, we observed plasmon-enhanced photocatalysis only for antenna-reactor complexes with antenna components of intermediate sizes (25 and 50 nm). Optimal photocatalytic performance was shown to be determined by a balance between maximized local field enhancements at the catalytically active Pt surface, minimized collective scattering of photons out of the catalyst bed by the complexes, and minimal light absorption in the Ag nanoparticle antenna. These results elucidate the critical aspects of local field enhancement, light scattering, and absorption in plasmonic photocatalyst design, especially under light-limited illumination conditions.

Ultrafast switching of surface plasmonic conditions in nonplasmonic metals

We demonstrate that ultrafast carrier excitation can drastically affect electronic structures and induce brief surface plasmonic response in non-plasmonic metals, potentially creating a plasmonic switch. Using first-principles molecular dynamics and Kubo-Greenwood formalism for laser-excited tungsten we show that carrier heating mobilizes d electrons into collective inter and intraband transitions leading to a sign flip in the imaginary optical conductivity, activating plasmonic properties for the initial non-plasmonic phase. The drive for the optical evolution can be visualized as an increasingly damped quasi-resonance at visible frequencies for pumping carriers across a chemical potential located in a d-band pseudo-gap with energy-dependent degree of occupation. The subsequent evolution of optical indices for the excited material is confirmed by time-resolved ultrafast ellipsometry. The large optical tunability extends the existence spectral domain of surface plasmons in ranges typically claimed in laser self-organized nanostructuring. Non-equilibrium heating is thus a strong factor for engineering optical control of evanescent excitation waves, particularly important in laser nanostructuring strategies.

Non-plasmonic metal nanoparticles as visible light photocatalysts for the selective oxidation of aliphatic alcohols with molecular oxygen at near ambient conditions.

Nanoparticles (NPs) of Pd and Pt were used for the selective oxidation of aliphatic alcohols with molecular oxygen as an oxidant at near ambient temperatures under visible light irradiation. Distinct final products were obtained under identical reaction conditions, aliphatic esters formed over the Pd NPs while aldehydes formed over the Pt NPs. The reason for this different product selectivity is proven to be due to the much stronger interaction of Pd NPs with alcohol and aldehyde compared to Pt NPs. The photocatalytic activity is tuneable by light intensity or a moderate change in the reaction temperature.

Plasmon-Enhanced Photocatalysis on TiO2-Passivated Gallium Phosphide

Integrating plasmon resonant nanostructures with photocatalytic semiconductors shows great promise for highly efficient photocatalytic processes1-4. However, the electrochemical instability of most III-V semiconductors severely limits their applicability in photocatlaysis. In this work, we passivate p-type GaP with a thin layer of n-type TiO2 using atomic layer deposition. The TiO2 passivation layer prevents corrosion of the GaP, as evidenced by atomic force microscopy and photoelectrochemical measurements. In addition, the TiO2 passivation layer provides an enhancement in photoconversion efficiency through the formation of a charge separating pn-region. Plasmonic Au nanoparticles deposited on top of the TiO2-passivated GaP further increases the photoconversion efficiency through local field enhancement. These two enhancement mechanisms are separated by systematically varying the thickness of the TiO2 layer. Because of the tradeoff between the quickly decaying plasmonic fields and the formation of the pn-charge separation region, an optimum performance is achieved for a TiO2 thickness of 0.5nm. Finite difference time domain (FDTD) simulations of the electric field profiles in this photocatalytic heterostructure corroborate these results. The effects of plasmonic enhancement are distinguished from the natural catalytic properties of Au by evaluating similar photocatalytic TiO2/GaP structures with catalytic, non-plasmonic metals (i.e., Pt) instead of Au. This general approach of passivating narrower band gap semiconductors enables a wider range of materials to be considered for plasmon-enhanced photocatalysis for high efficiency water splitting.1 Qiu, J., G. Zeng, P. Pavaskar, Z. Li and S.B. Cronin, Plasmon-Enhanced Water Splitting on TiO2-Passivated GaP Photocatalysts. Physical Chemistry Chemical Physics, 16, 3115 (2014).2 Hung, W.H., M. Aykol, D. Valley, W.B. Hou and S.B. Cronin, Plasmon Resonant Enhancement of Carbon Monoxide Catalysis. Nano Letters, 10, 1314-1318 (2010).3 Hou, W., Z. Liu, P. Pavaskar, W.H. Hung and S.B. Cronin, Plasmonic Enhancement of Photocatalytic Decomposition of Methyl Orange under Visible Light. J. Catal., 277, 149 (2011).4 Liu, Z., W. Hou, P. Pavaskar, M. Aykol and S. Cronin, Plasmon Resonant Enhancement of Photocatalytic Water Splitting Under Visible Illumination. Nano Letters, 11, 1111 (2011).

Plasmon-enhanced water splitting on TiO2-passivated GaP photocatalysts

Integrating plasmon resonant nanostructures with photocatalytic semiconductors shows great promise for high efficiency photocatalytic water splitting. However, the electrochemical instability of most III-V semiconductors severely limits their applicability in photocatalysis. In this work, we passivate p-type GaP with a thin layer of n-type TiO2 using atomic layer deposition. The TiO2 passivation layer prevents corrosion of the GaP, as evidenced by atomic force microscopy and photoelectrochemical measurements. In addition, the TiO2 passivation layer provides an enhancement in photoconversion efficiency through the formation of a charge separating pn-region. Plasmonic Au nanoparticles deposited on top of the TiO2-passivated GaP further increases the photoconversion efficiency through local field enhancement. These two enhancement mechanisms are separated by systematically varying the thickness of the TiO2 layer. Because of the tradeoff between the quickly decaying plasmonic fields and the formation of the pn-charge separation region, an optimum performance is achieved for a TiO2 thickness of 0.5 nm. Finite difference time domain (FDTD) simulations of the electric field profiles in this photocatalytic heterostructure corroborate these results. The effects of plasmonic enhancement are distinguished from the natural catalytic properties of Au by evaluating similar photocatalytic TiO2/GaP structures with catalytic, non-plasmonic metals (i.e., Pt) instead of Au. This general approach of passivating narrower band gap semiconductors enables a wider range of materials to be considered for plasmon-enhanced photocatalysis for high efficiency water splitting.

Nonplasmonic Metal Particles as Excitation Energy Transfer Acceptors: an Unexpected Efficiency Revealed by Quantum Mechanics

We present a time-dependent density functional theory investigation of the excitation energy transfer (EET) between a typical chromophore (perylene diimide) and a small metal cluster (Au20). Two different physical descriptions are tested for the metal: the real (nonplasmonic) cluster and a hypothetical nanoparticle characterized by a bulk gold dielectric response (which thus sustains surface plasmons). By comparing the results obtained for the same EET process with the two types of metal particles, we show that, surprisingly, nonplasmonic small metal clusters can be as intrinsically effective as plasmonic particles in EET, a finding that is also relevant for applications in several field ranging from analytical chemistry to nanoscience.