Volume 243, 2023

Catalytic reduction of dinitrogen to ammonia using molybdenum porphyrin complexes

Abstract

Porphyrin complexes are well-known in O2 and CO2 reduction, but their application to N2 reduction is less developed. Here, we show that oxo and nitrido complexes of molybdenum supported by tetramesitylporphyrin (TMP) are effective precatalysts for catalytic N2 reduction to ammonia, verified by 15N2 labeling studies and other control experiments. Spectroscopic and electrochemical studies illuminate some relevant thermodynamic parameters, including the N–H bond dissociation free energy of (TMP)MoNH (43 ± 2 kcal mol−1). We place these results in the context of other work on homogeneous N2 reduction catalysis.

Graphical abstract: Catalytic reduction of dinitrogen to ammonia using molybdenum porphyrin complexes

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
22 Nov 2022
Accepted
08 Dec 2022
First published
08 Dec 2022

Faraday Discuss., 2023,243, 429-449

Author version available

Catalytic reduction of dinitrogen to ammonia using molybdenum porphyrin complexes

A. S. Hegg, B. Q. Mercado, A. J. M. Miller and P. L. Holland, Faraday Discuss., 2023, 243, 429 DOI: 10.1039/D2FD00166G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements