Abstract
We report the use of fluorinated polymer zwitterions to build hybrid systems for efficient CO2 electroreduction. The unique combination of hydrophilic phosphorylcholine and hydrophobic fluorinated moieties in these polymers creates a fractal structure with mixed branched cylinders on the surface of gold nanoparticles (AuNPs). In the presence of these polymers, the CO faradaic efficiency improves by 50-80% in the range of −0.7 V to −0.9 V. The fractal structures have a domain size of ∼3 nm, showing enhanced mass transfer kinetics of CO2 approaching the catalyst surfaces without limiting ion diffusion. The phase-separated hydrophilic and hydrophobic domains offer separated channeling to water and CO2, as confirmed by attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and molecule dynamic (MD) simulations. H2O molecules permeate extensively into the polymer layer that adsorbs on zwitterions, forming continuous chains, while CO2 molecules strongly associate with the fluorinated tails of fluorinated polyzwitterions, with oxygen facing the positively charged amine groups. Overall, this coupling of zwitterion and fluorocarbon in a polymer material creates new opportunities for defining microenvironments of metallic nanocatalysts in hybrid structures.
| Original language | English |
|---|---|
| Pages (from-to) | 15558-15567 |
| Number of pages | 10 |
| Journal | Nanoscale |
| Volume | 16 |
| Issue number | 33 |
| DOIs | |
| State | Published - Jul 29 2024 |
Funding
JH is grateful for the financial support from the National Science Foundation (CHE 2102245 on CO reduction). PB acknowledges the support from the National Science Foundation (CBET 2144360 on simulation). TE acknowledges support for the synthesis of polymer zwitterions from the Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering (DE-SC0008876). The TEM images were obtained at the Biosciences Electron Microscopy Facility at the University of Connecticut. This work was also partially supported by the Green Emulsions Micelles and Surfactants (GEMS) Center of the University of Connecticut. The LiX beamline is part of the Center for BioMolecular Structure (CBMS), which is primarily supported by the National Institutes of Health, National Institute of General Medical Sciences (NIGMS) through a P30 Grant (P30GM133893), and by the DOE Office of Biological and Environmental Research (KP1605010). LiX also received additional support from NIH Grant S10 OD012331. As part of NSLS-II, a national user facility at Brookhaven National Laboratory, work performed at the CBMS is supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences Program under contract number DE-SC0012704. The computer simulations used resources of the National Energy Research Scientific Computing Center (NERSC) through allocation ERCAP0028612 and of the Advanced Cyberinfrastructure Coordination Ecosystem (ACCESS) through allocation CTS190069. 2
| Funders | Funder number |
|---|---|
| University of Connecticut | |
| Basic Energy Sciences | |
| U.S. Department of Energy | |
| Office of Science | |
| Biological and Environmental Research | KP1605010 |
| Office of Basic Energy Sciences Program | DE-SC0012704 |
| National Science Foundation | CBET 2144360, CHE 2102245 |
| National Institutes of Health | S10 OD012331 |
| National Institute of General Medical Sciences | P30GM133893 |
| Division of Materials Sciences and Engineering | DE-SC0008876 |