Electrocatalytic Dinitrogen Reduction to Ammonia Using Easily Reducible N-Fused Cobalt Porphyrins.

Autor: Ganesan A; University of North Texas, Chemistry, UNITED STATES OF AMERICA., Hajiseyedjavadi A; University of North Texas, Chemistry, UNITED STATES OF AMERICA., Rathi P; IIT Roorkee, Chemistry, INDIA., Kafle A; University of North Texas, Chemistry, UNITED STATES OF AMERICA., Adesope Q; University of North Texas, Chemistry, UNITED STATES OF AMERICA., Kumar S; IIT Roorkee, Chemistry, INDIA., Mesilov V; University of North Texas, Chemistry, INDIA., Kelber J; University of North Texas, Chemisitry, INDIA., Cundari T; University of North Texas, Chemistry, UNITED STATES OF AMERICA., Sankar M; IIT Roorkee, Chemistry, INDIA., D'Souza F; University of North Texas, Department of Chemistry, 1155, Union Circle, #305070, 76203-5017, Denton, UNITED STATES OF AMERICA.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jul 22, pp. e202402610. Date of Electronic Publication: 2024 Jul 22.
DOI: 10.1002/chem.202402610
Abstrakt: Single-site molecular electrocatalysts, especially those that perform catalytic conversion of N2 to NH3 under mild conditions, are highly desirable to derive fundamental structure-activity relations and as potential alternatives to the current energy-consuming Haber-Bosch ammonia production process. Combining theoretical calculations with experimental evidence, it has been shown that easily reducible cobalt porphyrins catalyze the six-electron, six-proton reduction of dinitrogen to NH3 at neutral pH and under ambient conditions. Two easily reducible N-fused cobalt porphyrins - CoNHF and CoNHF(Br)2 - reveal NRR activity with Faradic efficiencies between 6 - 7.5% with ammonia yield rates of 300 - 340 µmol g-1 h-1.  Contrary to this, much harder-to-reduce N-fused porphyrins - CoNHF(Ph)2 and CoNHF(PE)2 - reveal no NRR activity. The present study highlights the significance of tuning the redox and structural properties of single-site NRR electrocatalysts for improved NRR activity under mild conditions.
(© 2024 Wiley‐VCH GmbH.)
Databáze: MEDLINE
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