Issue 36, 2023

Why surface hydrophobicity promotes CO2 electroreduction: a case study of hydrophobic polymer N-heterocyclic carbenes

Abstract

We report the use of polymer N-heterocyclic carbenes (NHCs) to control the microenvironment surrounding metal nanocatalysts, thereby enhancing their catalytic performance in CO2 electroreduction. Three polymer NHC ligands were designed with different hydrophobicity: hydrophilic poly(ethylene oxide) (PEO–NHC), hydrophobic polystyrene (PS–NHC), and amphiphilic block copolymer (BCP) (PEO-b-PS–NHC). All three polymer NHCs exhibited enhanced reactivity of gold nanoparticles (AuNPs) during CO2 electroreduction by suppressing proton reduction. Notably, the incorporation of hydrophobic PS segments in both PS–NHC and PEO-b-PS–NHC led to a twofold increase in the partial current density for CO formation, as compared to the hydrophilic PEO–NHC. While polymer ligands did not hinder ion diffusion, their hydrophobicity altered the localized hydrogen bonding structures of water. This was confirmed experimentally and theoretically through attenuated total reflectance surface-enhanced infrared absorption spectroscopy and molecular dynamics simulation, demonstrating improved CO2 diffusion and subsequent reduction in the presence of hydrophobic polymers. Furthermore, NHCs exhibited reasonable stability under reductive conditions, preserving the structural integrity of AuNPs, unlike thiol-ended polymers. The combination of NHC binding motifs with hydrophobic polymers provides valuable insights into controlling the microenvironment of metal nanocatalysts, offering a bioinspired strategy for the design of artificial metalloenzymes.

Graphical abstract: Why surface hydrophobicity promotes CO2 electroreduction: a case study of hydrophobic polymer N-heterocyclic carbenes

Supplementary files

Article information

Article type
Edge Article
Submitted
25 maj 2023
Accepted
31 jul 2023
First published
08 aug 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 9664-9677

Why surface hydrophobicity promotes CO2 electroreduction: a case study of hydrophobic polymer N-heterocyclic carbenes

Q. Luo, H. Duan, M. C. McLaughlin, K. Wei, J. Tapia, J. A. Adewuyi, S. Shuster, M. Liaqat, Steven L. Suib, G. Ung, P. Bai, S. Sun and J. He, Chem. Sci., 2023, 14, 9664 DOI: 10.1039/D3SC02658B

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