Plasmonic antenna–reactor constructs for production of solar fuels and chemicals Ankit Dhankhar and Pramod P. Pillai* Department of Chemistry, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pashan, Pune – 411008, India Plasmonic metal nanoparticles (e.g., Ag, Al, Au, and Cu NPs) have emerged as an important class of photocatalysts because of their exceptionally high light absorption capabilities, which enable them to carry out various challenging chemical transformations. 1 However, their low intrinsic activity results in weak interactions with reactants and reaction intermediates, which presents fundamental limitations such as low yield and selectivity in sole plasmonic photocatalysis. 1,2 To address these challenges, researchers have developed strategies to enhance charge generation, separation, and extraction by optimizing catalyst-reactant interactions and designing plasmonic antenna-reactor systems with precise control over surface and reactor site engineering. 1-3 In my poster, I will be summarising our efforts in the design and photocatalytic properties of antenna–reactor constructs based on gold and rhodium. Three different morphologies of plasmonic gold-rhodium antenna– reactor constructs were developed: nanoflowers (AuNP-Rh NFs), dumbbell structures (AuNR-Rh DSs), and superstructures (AuNR-Rh SSs). 4,5 We achieved site-selective epitaxial growth of ordered rhodium islands on plasmonic gold nanorods (AuNR), with iodide ions playing a crucial role in spatially controlling nucleation and growth. The rational design of AuNR-Rh SSs led to the formation of uniform and spatially separated Rh islands with high-index facets on the surface of AuNR, promoting efficient light excitation and optimal hot charge carrier separation, alongside enhanced reactant adsorption and activation. 5 These antenna-reactor constructs were employed in the plasmon-driven photoregeneration of biological nicotinamide cofactors (NAD(P)H). The combination of the antenna-reactor effect and favorable catalyst-reactant interaction significantly boosts the photocatalytic activity of AuNP-Rh NFs and AuNR-Rh SSs, yielding ~30% and ~40% of enzymatically active 1,4-NAD(P)H cofactors, respectively. Further, AuNR-Rh SSs were utilized as photoelectrodes for plasmon- enhanced electrocatalytic water splitting and nitrate reduction, showcasing their potential in achieving sustainable energy solutions for the synthesis of value-added products. References 1. Linic, S. Chavez, R. Elias, Nat. Mater. 2021 , 20 , 916-924. 2. Jain, R. K. Kashyap, P. P. Pillai, Adv. Opt. Mater. 2022 ,10, 2200463. 3. Herran, A. Sousa-Castillo, C. Fan, S. Lee, W. Xie, M. Döblinger, B. Auguié, E. Cortés, Adv. Funct. Mater. 2022 , 2203418 . 4. Dhankhar, V. Jain, I. N. Chakraborty, P. P. Pillai, J. Photochem. Photobiol., A , 2023 , 437 , 114472. 5. Dhankhar, P. P. Pillai, Chem. Mater. 2024 , 36 , 10227–10237.
P131
© The Author(s), 2025
Made with FlippingBook Learn more on our blog