Photoinduced Electron and Energy Transfer Pathways and Photocatalytic Mechanisms in Hybrid Plasmonic Photocatalysis

Abstract

Hybrid plasmonic nanostructures are built on plasmonic metalnanostructures surrounded by catalytic metals or metal oxides. Recent studies have shown that hybrid plasmonic nanocatalysts can concurrently utilize thermal energy and photon stimuli and exhibit high catalytic activity, selectivity, and stability that are not attainable in conventional purely thermally activated catalytic processes. The hybrid plasmonic photocatalytic approach has recently emerged as an attractive concept for the conversion of solar energy into chemical energy, the distributed synthesis of valuable chemicals such as ammonia with little to no requirement of external heating, and the development of coke‐resistant and selective catalytic processes. The field of hybrid plasmonic photocatalysis has grown tremendously in the last decade. In this review article, the advantages of visible‐light‐augmented hybrid plasmonic photocatalysis over conventional pure thermally activated heterogeneous catalysis are discussed. Fundamental insights are provided into photocatalytic mechanisms by which the photoexcited charge carriers (electrons and holes) are formed and transferred to adsorbates triggering chemical transformations on the surface of hybrid plasmonic nanocatalysts. Computational modeling used for predicting and understanding the photocatalytic activity and selectivity on hybrid plasmonic nanostructures is also reviewed. The review closes with a discussion of the current challenges, new opportunities, and future outlook for hybrid plasmonic photocatalysis.

Cupric Oxide Mie Resonators

“…Hence, they enable trace-level/single molecule spectroscopy, − ultrasensitive light detection, , biosensing, and heat transfer. , In recent years, the development of optical antennas has mainly relied on plasmonic metal nanostructures (PMNs). Numerous applications of PMNs have been demonstrated, such as sensors, nano-, and micro-optical devices, photocatalysis, − and photovoltaics. − PMNs exhibit high extinction cross sections due to localized surface plasmon resonance (LSPR). ,− The LSPR frequency is sensitive to dielectric function and geometry (shape and size) of the nanostructure as well as the physical environment and EM coupling between neighboring nanostructures and substrates. , However, plasmonic resonators suffer from absorption losses inherent to metals at visible frequencies …”

Hybrid Plasmonic Nanomaterials for Hydrogen Generation and Carbon Dioxide Reduction

“…Finally, some reviews focus on particular reactions, such as the applications of plasmonic catalysts to organic transformations or the CO 2 reduction reaction (CO 2 RR) . Among the reviews on plasmon-assisted catalysis there are few on hybrid systems, so far mostly limited to bimetallic or plasmonic metal–semiconductor systems. − …”

Plasmonic Photocatalysis: Activating Chemical Bonds through Light and Plasmon

“…In this regard, "antenna-reactor" constructs have emerged as an effective system wherein the reactor catalyst material is incorporated as single or multiple atom sites on the surface of plasmonic NPs. [200][201][202][203][204][205][206][207][208][209][210][211][212][213][214][215][216][217][218][219] Pd, Ru, Pt, and Ir metals are commonly used as the reactor catalyst component in the "antenna-reactor" constructs, because of their superior molecular adsorption and catalytic properties over plasmonic NPs. [214][215][216][217][218] In such a design, the antenna effect of plasmonic NPs can lead to the formation of forced plasmon in non-plasmonic reactive sites (predominantly via interband transition), thereby creating charge carriers in the reactive sites.…”

“…[200][201][202][203][204][205][206][207][208][209][210][211][212][213][214][215][216][217][218][219] Pd, Ru, Pt, and Ir metals are commonly used as the reactor catalyst component in the "antenna-reactor" constructs, because of their superior molecular adsorption and catalytic properties over plasmonic NPs. [214][215][216][217][218] In such a design, the antenna effect of plasmonic NPs can lead to the formation of forced plasmon in non-plasmonic reactive sites (predominantly via interband transition), thereby creating charge carriers in the reactive sites. The following section will discuss the potency of plasmonic antennareactor nanocomposites in driving challenging and industrially relevant chemical reactions.…”