Highly Efficient Carbon Dioxide Electroreduction via DNA-Directed Catalyst Immobilization
Name
fan-et-al-2024-highly-efficient-carbon-dioxide-electroreduction-via-dna-directed-catalyst-immobilization.pdf
Description
Published version
Size
3.81 MB
Format
Adobe PDF
Checksum (MD5)
c21d47368dcfe397a0af8db24653149a
Author(s)
Fan, Gang
Corbin, Nathan
Chung, Minju
Gill, Thomas M
Moore, Evan B
Karbelkar, Amruta A
Furst, Ariel L
Date Issued
April 22, 2024
Journal
JACS Au
Publisher
American Chemical Society
Citation
JACS Au 2024, 4, 4, 1413–1421
Version
Final published version
Abstract
Electrochemical reduction of carbon dioxide (CO2) is a promising route to up-convert this industrial byproduct. However, to perform this reaction with a small-molecule catalyst, the catalyst must be proximal to an electrode surface. Efforts to immobilize molecular catalysts on electrodes have been stymied by the need to optimize the immobilization chemistries on a case-by-case basis. Taking inspiration from nature, we applied DNA as a molecular-scale "Velcro" to investigate the tethering of three porphyrin-based catalysts to electrodes. This tethering strategy improved both the stability of the catalysts and their Faradaic efficiencies (FEs). DNA-catalyst conjugates were immobilized on screen-printed carbon and carbon paper electrodes via DNA hybridization with nearly 100% efficiency. Following immobilization, a higher catalyst stability at relevant potentials is observed. Additionally, lower overpotentials are required for the generation of carbon monoxide (CO). Finally, high FE for CO generation was observed with the DNA-immobilized catalysts as compared to the unmodified small-molecule systems, as high as 79.1% FE for CO at -0.95 V vs SHE using a DNA-tethered catalyst. This work demonstrates the potential of DNA "Velcro" as a powerful strategy for catalyst immobilization. Here, we demonstrated improved catalytic characteristics of molecular catalysts for CO2 valorization, but this strategy is anticipated to be generalizable to any reaction that proceeds in aqueous solutions.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Center for Environmental Health Sciences
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivatives
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/jacsau.3c00823
