Poly(ionic liquid) nanovesicles via polymerization induced self-assembly and their stabilization of Cu nanoparticles for tailored CO2 electroreduction

Herein, we report a straightforward, scalable synthetic route towards poly(ionic liquid) (PIL) homopoly-mer nanovesicles (NVs) with a tunable particle size of 50 to 120 nm and a shell thickness of 15 to 60 nm via one-step free radical polymerization induced self-assembly. By increasing monomer concentration for polymerization, their nanoscopic morphology can evolve from hollow NVs to dense spheres, and finally to directional worms, in which a multilamellar packing of PIL chains occurred in all samples. The trans-formation mechanism of NVs' internal morphology is studied in detail by coarse-grained simulations, revealing a correlation between the PIL chain length and the shell thickness of NVs. To explore their potential applications, PIL NVs with varied shell thickness are in situ functionalized with ultra-small (1 ti 3 nm in size) copper nanoparticles (CuNPs) and employed as electrocatalysts for CO2 electroreduc-tion. The composite electrocatalysts exhibit a 2.5-fold enhancement in selectivity towards C1 products (e.g., CH4), compared to the pristine CuNPs. This enhancement is attributed to the strong electronic interactions between the CuNPs and the surface functionalities of PIL NVs. This study casts new aspects on using nanostructured PILs as new electrocatalyst supports in CO2 conversion to C1 products.(c) 2023 Published by Elsevier Inc.

Automated summary

In this study, a straightforward and scalable synthetic route was developed to fabricate poly(ionic liquid) (PIL) homopolymer nanovesicles (NVs) with tunable particle size and shell thickness. By increasing the monomer concentration, the morphology of the NVs changed from hollow structures to dense spheres and then to directional worms. The internal morphology transformation of NVs was investigated using simulations, which revealed a correlation between PIL chain length and NVs shell thickness. The functionalized PIL NVs were employed as electrocatalysts for CO2 electroreduction and exhibited enhanced selectivity towards C1 products due to strong electronic interactions with ultra-small copper nanoparticles (CuNPs).