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Porous Plasmonic Nanoparticles on Multi-Dimensional Organic Porous Polymers for Selective Sonophotocatalytic Valorization of Lignin Model Compounds

Abstract

Localized surface plasmon resonance (LSPR) occurring in metal nanoparticles has opened the door to fascinating concepts in light-mediated catalysis, i.e., photocatalysis. In this project, we investigate an interesting, yet rarely explored, feature with great potential for the creation of plasmonic nanostructures with novel functionalities, i.e., porosity. We establish simple, scalable routes to produce porous plasmonic nanoparticles of abundant and inexpensive non-noble metals with controlled dimension. We utilize these nanostructures in the emerging field of sonophotocatalysis: the sound- and light-mediated catalysis, for hydrogen production and biomass valorization into platform chemicals. 


Plasmonic nanoparticles can act as deep sub-wavelength lenses by focusing light at their surface electromagnetic fields in the nanoparticles vicinity whose intensity is several times higher than the incoming light’s. To strengthen the local electromagnetic field with respect to the incoming field, we can produce intramaterial nanogaps (i.e., the pores) to give rise to the so-called​“hotspots” regions. The availability of accessible hotspots combined with large surface-to-volume ratios makes porous metal nanoparticles uniquely suited for plasmon-mediated photocatalysis. The nanoarchitecture-dependent optical properties of plasmonic nanomaterials would provide unique opportunities for better utilization of light and modulating the material properties that dictate the course of photocatalytic reactions at surface. 
 

In this project, carefully designed porous plasmonic nanoparticles are coupled with carbonaceous porous photocatalysts, such as the well-known graphitic carbon nitride and those prepared from lignocellulosic or sea food-based organic wastes. The fundamental insights into the atomic- and nano-scale architectures are elucidated using state-of-the-art structure-determining techniques. The behavior of photogenerated charge carriers in ultrafast regimes, e.g., due to the ultrafast​“hot” electron dynamics (transfer/​injection) in the formed plasmonic nanoarchitecures, is characterized with transient spectroscopy. The photocatalytic performance is assessed for hydrogen evolution and transformation of lignin model compounds to establish structure-activity relationships. Once established, the new insights extracted from this project can be utilized to design innovative and unique photocatalyst architectures with better performances. 
 

Project title: Porous Plasmonic Nanoparticles on Multi-Dimensional Organic Porous Polymers for Selective Sonophotocatalytic Valorization of Lignin Model Compounds.

Financial Support: The Ulam Programme from the Polish National Agency for Academic Exchange (BPN/ULM/2022/1/00009).

Host Institute: Institute of Physical Chemistry, Polish Academy of Sciences.

Postdoctoral Fellow: Hanggara Sudrajat, Ph.D.

Supervisor: Prof. Juan Carlos Colmenares. 

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