Plasmonic Catalysis

From Fundamentals to Applications

Pedro H.C. Camargo, Emiliano Cortés, Pedro H.C. Camargo, Emiliano Cortés, Pedro H.C. Camargo, Emiliano Cortés

• Publisher: Wiley-VCH
• Year: 2021
• Print ISBN:
  9783527347506
• Edition: 1
• eBook ISBN:
  9783527826964
• Topic: Technology & Engineering
• Subtopic: Materials Science
• Index: Technology & Engineering

Explore this comprehensive discussion of the foundational and advanced topics in plasmonic catalysis from two leaders in the field  

Plasmonic Catalysis: From Fundamentals to Applications delivers a thorough treatment of plasmonic catalysis, from its theoretical foundations to myriad applications in industry and academia. In addition to the fundamentals, the book covers the theory, properties, synthesis, and various reaction types of plasmonic catalysis. It also covers its applications in reactions including oxidation, reduction, nitrogen fixation, CO2 reduction, and more.  

The book characterizes plasmonic catalytic systems and describes their properties, tackling the integration of conventional methods as well as new methods able to unravel the optical, electronic, and chemical properties of these systems. It also describes the fundamentals of controlled synthesis of metal nanoparticles relevant to plasmonic catalysis, as well as practical examples thereof. 

Plasmonic Catalysis covers a wide variety of other practical topics in the field, including hydrogenation reactions and the harvesting of LSPR-excited charge carriers. Readers will also benefit from the inclusion of:  

• A thorough introduction to plasmonic catalysis, a theory of plasmons for catalysis and mechanisms, as well as optical properties of plasmonic-catalytic nanostructures 
• An exploration of the synthesis of plasmonic nanoparticles for photo and electro catalysis, as well as plasmonic catalysis towards oxidation reactions and hydrogenation reactions 
• Discussions of plasmonic catalysis for multi-electron processes and artificial photosynthesis and N2 fixation 
• An examination of control over reaction selectivity in plasmonic catalysis  

Perfect for catalytic chemists, materials scientists, photochemists, and physical chemists, Plasmonic Catalysis: From Fundamentals to Applications will also earn a place in the libraries of physicists who seek a one-stop resource to enhance their understanding of applications in plasmonic catalysis. 

1
Theory of Plasmonic Excitations: Fundamentals and Applications in Photocatalysis

Lucas V. Besteiro^1,2, Xiang-Tian Kong¹, Zhiming M. Wang¹ and Alexander O. Govorov^1,3

¹Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, China

²Institut National de la Recherche Scientifique, Centre Énergie, Matériaux et Télécommunications, Varennes, QC, Canada

³Department of Physics and Astronomy, Ohio University, Athens, OH, USA

1.1 Introduction

Plasmonic systems have become a common tool in a variety of subfields of nanotechnology, be it to manipulate the propagation of light or to harvest its energy. The fundamental properties that make them attractive and versatile are their large interaction cross-sections and a great degree of spectral tunability, both arising from the resonant nature of their interaction with light [1]. We can therefore use them as nanoantennas capable of effectively controlling the flow of light at frequencies ranging from the ultraviolet (UV) to the infrared (IR). Although, historically, a good amount of interest in plasmonics was directed toward creating optical metamaterials [2, 3], the fundamentally lossy nature of plasmonic materials, such as noble metals, introduced practical limits on their use in optical devices [4]. This invited many researchers to find ways for taking advantage of the nonradiative losses of plasmonic systems [5, 6]. Some examples include their usage as photoheaters [7–10], photodetectors [6, 11–13], or, most relevantly to the contents of this book, as photosensitizing elements in photocatalysis and photoelectrochemistry [14–22]. In order to understand why plasmonic nanoparticles (NPs) are of interest in the context of chemical catalysis, we should explore the fundamental properties of metallic materials, and how these impact their interaction with light and with their environment, so that they can drive chemical reactions. In this chapter, we will discuss the above points, providing a general theoretical perspective of the dynamics of plasmonic excitation in NPs, and the mechanisms by which energy can be transferred from a coherent plasmonic oscillation to the environment.

Before commencing a detailed description of the internal dynamics in plasmonic systems, it would be convenient to contrast the fundamental properties of these materials with those of semiconductors, more conventional heterogeneous photocatalysts [24]. In doing so, we will highlight the relevance of electronic structure in determining the optical properties of a given material. Semiconductors are crystalline solids, and the periodicity of their structure gives rise to bands with a continuum of electronic states. These bands are key quantum properties of the periodic lattice of a crystal, and contrast with the discrete electronic states in atoms and molecules. A schematic representation of this can be seen in Figure 1.1a, which depicts the electronic structure of a typical bulk semiconductor, showcasing also its characteristic bandgap separating occupied and unoccupied states. Optical transitions can excite electrons across the bandgap, generating relatively long-lived electron–hole pairs that can drive surface chemistry in photocatalytic systems, targeting different redox reactions depending on their relative energy alignment with the valence or conduction band of the semiconductor. They are widely used in photoelectrochemical cells [25, 26] and other photocatalytic setups [27, 28], employing both bulk and nanostructured semiconductor materials as a repository of optically excited charge carriers for driving the target reaction. These long-lived carriers can be extracted via contacts since semiconductors, when doped, possess high conductivities and are suitable for building electrochemical circuits [25, 29]. At the same time, the bandgap introduces a threshold on the energy of the photons that can be absorbed, which limits the fraction of the solar spectrum available for conversion. This shortcoming of semiconductors as photocatalysts under solar irradiation has been one of the motivations for combining them with plasmonic systems [15].

Figure 1.1 Schematic representation of the typical electronic states in two relevant types of materials used in heterogeneous photocatalysis: (a) semiconductors and (b) plasmonic crystals. The diagrams include the main optical excitation cha...

Table of contents

• Cover
• Table of Contents
• Title Page
• Copyright
• Prologue
• Introduction
• 1 Theory of Plasmonic Excitations
• 2 Characterization and Properties of Plasmonic-Catalytic Nanostructures from the Atomic Scale to the Reactor Scale
• 3 Synthesis of Plasmonic Nanoparticles for Photo- and Electrocatalysis
• 4 Plasmonic Catalysis Toward Hydrogenation Reactions
• 5 Plasmonic Catalysis, Photoredox Chemistry, and Photosynthesis
• 6 Plasmonic Catalysis for N2 Fixation
• 7 Untangling Thermal and Nonthermal Effects in Plasmonic Photocatalysis
• 8 Earth-Abundant Plasmonic Catalysts
• 9 Plasmon-Enhanced Electrocatalysis
• 10 Plasmonic Metal/Semiconductor Heterostructures
• Epilogue
• Index
• End User License Agreement