The successful development of artificial photosynthesis requires finding new materials able to efficiently harvest sunlight and catalyze hydrogen generation and carbon dioxide reduction reactions. Plasmonic nanoparticles are promising candidates for these tasks, due to their ability to confine solar energy into molecular regions. Here, we review recent developments in hybrid plasmonic photocatalysis, including the combination of plasmonic nanomaterials with catalytic metals, semiconductors, perovskites, 2D materials, metal–organic frameworks, and electrochemical cells. We perform a quantitative comparison of the demonstrated activity and selectivity of these materials for solar fuel generation in the liquid phase. In this way, we critically assess the state-of-the-art of hybrid plasmonic photocatalysts for solar fuel production, allowing its benchmarking against other existing heterogeneous catalysts. Our analysis allows the identification of the best performing plasmonic systems, useful to design a new generation of plasmonic catalysts.

Atomically dispersed transition metals on carbon-based aromatic substrates are an emerging class of electrocatalysts for the electroreduction of CO2. However, electron delocalization of the metal site with the carbon support via d-π conjugation strongly hinders CO2 activation at the active metal centers. Herein, we introduce a strategy to attenuate the d-π conjugation at single Ni atomic sites by functionalizing the support with cyano moieties. In situ attenuated total reflection infrared spectroscopy and theoretical calculations demonstrate that this strategy increases the electron density around the metal centers and facilitates CO2 activation. As a result, for the electroreduction of CO2 to CO in aqueous KHCO3 electrolyte, the cyano-modified catalyst exhibits a turnover frequency of ~22,000 per hour at −1.178 V versus the reversible hydrogen electrode (RHE) and maintains a Faradaic efficiency (FE) above 90% even with a CO2 concentration of only 30% in an H-type cell. In a flow cell under pure CO2 at −0.93 V versus RHE the cyano-modified catalyst enables a current density of −300 mA/cm2 with a FE above 90%.

Hybrid nanoparticles combining plasmonic and catalytic components have recently gained interest for their potential use in sunlight‐to‐chemical energy conversion. However, a deep understanding of the structure–performance that maximizes the use of the incoming energy remains elusive. Here, a suite of Au and Pd based nanostructures in core–shell and core‐satellites configurations are designed and their photocatalytic activity for Hydrogen (H2) generation under sunlight illumination is tested. Formic acid is employed as H2 source. Core‐satellite systems show a higher enhancement of the reaction upon illumination, compared to core–shell ones. Electromagnetic simulations reveal that a key difference between both configurations is the excitation of highly localized and asymmetric electric fields in the gap between both materials. In this scheme, the core Au particle acts as an antenna, efficiently capturing visible light via the excitation of localized plasmon resonances, while the surrounding Pd satellites transduce the locally‐enhanced electric field into catalytic activity. These findings advance the understanding of plasmon‐driven photocatalysis, and provide an important benchmark to guide the design of the next generation of plasmonic bimetallic nanostructures.

Arsenic is one of the most toxic elements in natural waters since prolonged exposure to this metalloid can cause chronic damage to health. Its removal from ground-water remains one of...