Eco-friendly and biocompatible gelatin plasmonic filters for UV-vis-NIR light.

The quest for environmentally sustainable materials spans many fields and applications including optical materials. Here, we present the development of light filters using a gelatin-based nanocomposite. Owing to the plasmonic properties of metallic nanoparticles (NPs), strong light-matter interactions, these filters can be customized across the UV-Visible-NIR spectrum. The filters are designed for modular use, allowing for the addition or removal of desired spectral ranges. Moreover, the nanocomposites are composed of biodegradable and biocompatible materials which highlight the intersection of chemistry and ecological awareness for the exploration of new eco-friendly alternatives. These plasmonic gelatin-based filters block light due to the Localized Surface Plasmon Resonance (LSPR) of the NPs and can be tailored to meet various requirements, akin to a diner selecting options from a menu. This approach is inspired by culinary techniques, and we anticipate it will stimulate further exploration of biomaterials for applications in optics, materials science or electronics.

Balancing Near-Field Enhancement and Hot Carrier Injection: Plasmonic Photocatalysis in Energy-Transfer Cascade Assemblies.

Photocatalysis stands as a very promising alternative to photovoltaics in exploiting solar energy and storing it in chemical products through a single-step process. A central obstacle to its broad implementation is its low conversion efficiency, motivating research in different fields to bring about a breakthrough in this technology. Using plasmonic materials to photosensitize traditional semiconductor photocatalysts is a popular strategy whose full potential is yet to be fully exploited. In this work, we use CdS quantum dots as a bridge system, reaping energy from Au nanostructures and delivering it to TiO2 nanoparticles serving as catalytic centers. The quantum dots can do this by becoming an intermediate step in a charge-transfer cascade initiated in the plasmonic system or by creating an electron-hole pair at an improved rate due to their interaction with the enhanced near-field created by the plasmonic nanoparticles. Our results show a significant acceleration in the reaction upon combining these elements in hybrid colloidal photocatalysts that promote the role of the near-field enhancement effect, and we show how to engineer complexes exploiting this approach. In doing so, we also explore the complex interplay between the different mechanisms involved in the photocatalytic process, highlighting the importance of the Au nanoparticles' morphology in their photosensitizing capabilities.

Synergistic Combination of Charge Carriers and Energy-Transfer Processes in Plasmonic Photocatalysis.

Important efforts are currently under way in order to develop further the nascent field of plasmonic photocatalysis, striving for improved efficiencies and selectivities. A significant fraction of such efforts has been focused on distinguishing, understanding, and enhancing specific energy-transfer mechanisms from plasmonic nanostructures to their environment. Herein, we report a synthetic strategy that combines two of the main physical mechanisms driving plasmonic photocatalysis into an engineered system by rationally combining the photochemical features of energetic charge carriers and the electromagnetic field enhancement inherent to the plasmonic excitation. We do so by creating hybrid photocatalysts that integrate multiple plasmonic resonators in a single entity, controlling their joint contribution through spectral separation and differential surface functionalization. This strategy allows us to create complex hybrids with improved photosensitization capabilities, thanks to the synergistic combination of two photosensitization mechanisms. Our results show that the hot electron injection can be combined with an energy-transfer process mediated by the near-field interaction, leading to a significant increase in the final photocatalytic response of the material and moving the field of plasmonic photocatalysis closer to energy-efficient applications. Furthermore, our multimodal hybrids offer a test system to probe the properties of the two targeted mechanisms in energy-related applications such as the photocatalytic generation of hydrogen and open the door to wavelength-selective photocatalysis and novel tandem reactions.

Plasmonic photocatalysis in aqueous solution: assessing the contribution of thermal effects and evaluating the role of photogenerated ROS.

Plasmon-induced photocatalysis can drive photochemical processes with an unprecedented control of reactivity, using light as sole energy source. Nevertheless, disentangling the relative importance of thermal and non-thermal features upon plasmonic excitation remains a difficult task. In this work we intend to separate the role played by the photogenerated charge carriers from thermal mechanisms in the plasmonic photo-oxidation of a model organic substrate in aqueous solution and using a metal-semiconductor hybrid as model photocatalyst. Accordingly, we present a simple set of experimental procedures and simulations that allow us to discard the thermal dissipation upon plasmonic excitation as the main driving force behind these chemical reactions. Moreover, we also study the photogeneration of reactive oxygen species (ROS), discussing their fundamental role in photo-oxidation reactions and the information they provide regarding the reactivity of the photogenerated electrons and holes.

Chiral Generation of Hot Carriers for Polarization-Sensitive Plasmonic Photocatalysis.

Mastering the manipulation of chirality at the nanoscale has long been a priority for chemists, physicists, and materials scientists, given its importance in the biochemical processes of the natural world and in the development of novel technologies. In this vein, the formation of novel metamaterials and sensing platforms resulting from the synergic combination of chirality and plasmonics has opened new avenues in nano-optics. Recently, the implementation of chiral plasmonic nanostructures in photocatalysis has been proposed theoretically as a means to drive polarization-dependent photochemistry. In the present work, we demonstrate that the use of inorganic nanometric chiral templates for the controlled assembly of Au and TiO2 nanoparticles leads to the formation of plasmon-based photocatalysts with polarization-dependent reactivity. The formation of plasmonic assemblies with chiroptical activities induces the asymmetric formation of hot electrons and holes generated via electromagnetic excitation, opening the door to novel photocatalytic and optoelectronic features. More precisely, we demonstrate that the reaction yield can be improved when the helicity of the circularly polarized light used to activate the plasmonic component matches the handedness of the chiral substrate. Our approach may enable new applications in the fields of chirality and photocatalysis, particularly toward plasmon-induced chiral photochemistry.

Titanate Nanowires as One-Dimensional Hot Spot Generators for Broadband Au-TiO2 Photocatalysis.

Metal-semiconductor nanocomposites have become interesting materials for the development of new photocatalytic hybrids. Along these lines, plasmonic nanoparticles have proven to be particularly efficient photosensitizers due to their ability to transfer plasmonic hot electrons onto large bandgap semiconductors such as TiO2, thus extending the activity of the latter into a broader range of the electromagnetic spectrum. The extent of this photosensitization process can be substantially enhanced in those geometries in which high electromagnetic fields are created at the metal-semiconductor interface. In this manner, the formation of plasmonic hot spots can be used as a versatile tool to engineer the photosensitization process in this family of hybrid materials. Herein, we introduce the use of titanate nanowires as ideal substrates for the assembly of Au nanorods and TiO2 nanoparticles, leading to the formation of robust hybrids with improved photocatalytic properties. Our approach shows that the correct choice of the individual units together with their rational assembly are of paramount importance in the development of complex nanostructures with advanced functionalities.