POS6-0762
Photocatalytic Polymer Nanoparticles with Localized Pyridine Microenvironments for Selective CO2-to-Formate Conversion
Topic
S6. Emerging Polymer and Hybrid Materials for Advanced Energy Storage and Conversion
When and Where
Oct 1, 2026
08:30 - 09:30
Room 301 (Grand Ballroom)
Session Chairs
Jinkee HONG
Ki Su KIM
Presenter(s)
Juwon Ha (DGIST)
Co-Author(s)
Abstract
Photocatalytic CO2 reduction to formate is a promising carbon utilization strategy, but conventional one-electron pathways are constrained by the high-energy CO2•− intermediate, which limits visible light utilization and promotes unproductive side reactions. Pyridine-mediated pathways circumvent this thermodynamically demanding radical route through sequential proton-coupled electron transfer (PCET), forming a dihydropyridine intermediate that directly delivers a hydride to CO2. To further enhance this pyridine-mediated pathway, we construct a tailored catalytic microenvironment around photocatalytic polymer nanoparticles by using poly(4-vinylpyridine)-block-poly(N,N-dimethylacrylamide) (P4VP-b-PDMA) as a functional dispersant, creating a core–corona architecture with a photocatalytic core and a pyridine-rich polymer corona. We propose that localized pyridine enrichment near the photocatalyst surface facilitates rapid photoinduced electron transfer to pyridine, thereby suppressing exciton recombination and promoting sequential two-electron reduction to form hydride-donating dihydropyridine intermediates. Control experiments will examine the role of pyridine localization near the photocatalytic core in enhancing the efficiency of the two-electron reduction process. Under visible light irradiation (λmax < 500 nm, 1 atm CO2), this polymer photocatalysts will be evaluated for efficient formate production under CO2-saturated aqueous conditions, with target formate concentrations on the order of 10 mM and performance benchmarked by production rate, apparent quantum yield (AQY), selectivity, and long-term stability. The dense P4VP interface is expected to enhance the local probability of hydride-transfer events, while the PDMA chains maintain colloidal stability under reaction conditions. This functional polymer-corona strategy offers a versatile platform for engineering microenvironments that promote selective solar-to-chemical conversion.
