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

Autor: Ganesan A; Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton TX, 76203-5017, USA., Hajiseyedjavadi A; Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton TX, 76203-5017, USA., Rathi P; Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India., Kafle A; Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton TX, 76203-5017, USA., Adesope Q; Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton TX, 76203-5017, USA., Kumar S; Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India., Mesilov V; Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton TX, 76203-5017, USA., Kelber JA; Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton TX, 76203-5017, USA., Cundari TR; Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton TX, 76203-5017, USA., Sankar M; Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India., D'Souza F; Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton TX, 76203-5017, USA.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Oct 17; Vol. 30 (58), pp. e202402610. Date of Electronic Publication: 2024 Sep 17.
DOI: 10.1002/chem.202402610
Abstrakt: Single-site molecular electrocatalysts, especially those that perform catalytic conversion of N 2 to NH 3 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 NH 3 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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