Title :

Black Gold Based “Antenna-Reactor” of Nickel: Concept of Forced Plasmon to Activate Non-plasmonic Metal Catalysts

Abstract :

Localized surface plasmon resonance (LSPR) allows metal nanoparticles (NPs) to harvest light and concentrate it near the nanoparticle surface. Light energy is then utilized in the generation of excited charge carriers as well as heat. Plasmonic catalysts used these energetic charge carriers (and the heat) to drive chemical transformations on their surface and allowed the discovery of novel and selective reaction pathways that were not possible in thermal catalysis1-3. However, since the number of metals that show plasmon absorption in the visible range is limited, the reactions that can be catalyzed by these metals are also limited. Using the concept of multicomponent plasmonic catalysis, one can design a hybrid catalyst by combining plasmonic metals with non-plasmonic but active catalytic metals in close proximity to each other, named as “antenna-reactor”4.           

   In this work, we have designed and synthesized dendritic plasmonic colloidosomes (DPCs), known as Black Gold5 based “Antena Reactor” of Nickel (DPC-Ni).When DPC-Ni was illuminated with visible light, the plasmonic metal antenna of Au undergo LSPR and non-radiative Landau damping induces an optical polarization in non-plasmonic Ni metal (reactor) by creating a flow of plasmon energy from the antenna (Au) to the reactor (Ni). This created plasmon on non-plasmonic Ni metal (forced plasmon), which then undergo decay to generate hot charge carriers (electrons and holes). The forced plasmon made the reactor Ni catalytically active and it was able to catalyze several challenging reactions (H2 dissociation, propene reduction, and C-Cl bond activation) using visible light at room temperature, which generally need high temperature and pressure. In this talk, I will present the synthesis of DPC-Ni, their characterizations, application in catalysis and preliminary insights into the reaction mechanism and electron dynamics of DPC-Ni catalyst.

 

References:

1. Aslam, U.; Rao, V. G.; Chavez, S.; Linic, S. Catalytic conversion of solar to chemical energy on plasmonic metal nanostructures. Nat. Catal. 2018, 1, 656−665

2. Gelle, A.; Jin, T.; de la Garza, L.; Price, G. D.; Besteiro, L. V.; Moores, A. Applications of Plasmon-Enhanced Nanocatalysis to Organic Transformations. Chem. Rev. 2020, 120, 986−1041

3.  Zhan, C.; Chen, J. X.; Yi, J.; Li, F. J.; Wu, D. Y.; Tian, Z. Q. From Plasmon-Enhanced Molecular Spectroscopy to Plasmon Mediated Chemical Reactions. Nat. Rev. Chem. 2018, 2, 216−230.

4. Halas, J. N. et al. Heterometallic Antenna−Reactor Complexes for Photocatalysis. Proc. Natl. Acad. Sci. U.S.A. 2016, 113, 8916–8920.

5. Polshettiwar etl al. Plasmonic Colloidosomes of Black Gold for Solar Energy Harvesting and Hotspots Directed Catalysis for CO2 to Fuel Conversion. Chemical Science, 2019, 10, 6594-6603.