Photodriven Ammonia Synthesis from Manganese Nitrides: Photophysics and Mechanistic Investigations

Panetti, Grace B.; Kim, Junho; Myong, Michele S.; Bird, Matthew J.; Scholes, Gregory D.; Chirik, Paul J.

doi:10.1021/jacs.4c08795

Title: Photodriven Ammonia Synthesis from Manganese Nitrides: Photophysics and Mechanistic Investigations

Journal Article · 27 September 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c08795 · OSTI ID:2448532

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Princeton University, NJ (United States); Princeton University
Princeton University, NJ (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Ammonia synthesis from N,N,O,O-supported manganese(V) nitrides and 9,10-dihydroacridine using proton-coupled electron transfer and visible light irradiation in the absence of precious metal photocatalysts is described. While the reactivity of the nitride correlated with increased absorption of blue light, excited-state lifetimes determined by transient absorption were on the order of picoseconds. Furthermore, this eliminated excited-state manganese nitrides as responsible for bimolecular N–H bond formation. Spectroscopic measurements on the hydrogen source, dihydroacridine, demonstrated that photooxidation of 9,10-dihydroacridine was necessary for productive ammonia synthesis. Transient absorption and pulse radiolysis data for dihydroacridine provided evidence for the presence of intermediates with weak E–H bonds, including the dihydroacridinium radical cation and both isomers of the monohydroacridine radical, but notably these intermediates were unreactive toward hydrogen atom transfer and net N–H bond formation. Additional optimization of the reaction conditions using higher photon flux resulted in higher rates of the ammonia production from the manganese(V) nitrides due to increased activation of the dihydroacridine.

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Research Organization:: BioLEC EFRC, Princeton, NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0019370; SC0006498; SC0012704

OSTI ID:: 2448532

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 40 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Photodriven Ammonia Synthesis from Manganese Nitrides: Photophysics and Mechanistic Investigations

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