Configuration Engineering of Plasmonic-Metal/Semiconductor Nanohybrids for Solar Fuel Production†

Solar fuel production, which primarily focuses on harnessing solar energy to convert CO₂ into fuels or produce H₂ through water splitting, holds transformative potential for addressing global energy demands and environmental challenges. However, several obstacles still need to be overcome, particularly concerning the efficiency and scalability of solar fuel systems. Plasmonic-metal/semiconductor nanohybrids (PSNs) represent a cutting-edge class of photocatalysts designed to overcome current efficiency bottlenecks by merging the unique localized surface plasmon resonance (LSPR) properties of plasmonic metals with the catalytic efficiency of semiconductors, thereby enhancing the overall efficiency of light-driven solar-to-fuel conversion. Precise regulation of PSN structures is essential for guiding the extraction and flow of energy and charge carriers within the nanohybrids, which ultimately determines their photocatalytic performance. In this perspective, we aim to highlight the direct impact that the configuration of these nanohybrids has on the efficiency of solar fuel production through various triggered plasmonic energy transfer mechanisms. To this end, we begin with a brief introduction to the basic plasmonic effects and fundamental energy transfer mechanisms between plasmonic metals and semiconductors. We then provide representative examples of how PSNs with five categories of engineered configurations (namely, core–shell, yolk–shell, Janus/heterodimer/dumbbell, core–satellite, and other hierarchical structures) enhance solar fuel production through three primary mechanisms: plasmon-induced resonance energy transfer, light absorption/trapping, and hot electron injection. We conclude this Perspective by outlining the remaining challenges and research directions in this field.