Spontaneous N2 formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia

Trenerry, Michael J.; Wallen, Christian M.; Brown, Tristan R.; Park, Sungho V.; Berry, John F.

doi:10.1038/s41557-021-00797-w

Spontaneous N₂ formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia

Journal Article · Sun Nov 07 23:00:00 EST 2021 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-021-00797-w· OSTI ID:1835257

Trenerry, Michael J. ^[1]; ^[2]; Brown, Tristan R. ^[2]; ^[2]; ^[2]

Univ. of Wisconsin, Madison, WI (United States); University of Wisconsin, Madison
Univ. of Wisconsin, Madison, WI (United States)

The electrochemical conversion of ammonia to dinitrogen in a direct ammonia fuel cell (DAFC) is a necessary technology for the realization of a Nitrogen Economy. Previous efforts to catalyze this reaction with molecular complexes require the addition of exogenous oxidizing reagents or application of potentials greater than the thermodynamic potential for the oxygen reduction reaction (ORR) – the cathodic process of a DAFC. We report a stable metal–metal bonded diruthenium complex that spontaneously produces dinitrogen from ammonia under ambient conditions. The resulting reduced diruthenium material can be re-oxidized with oxygen for subsequent reactions with ammonia, demonstrating its ability to spontaneously promote both half reactions necessary for a DAFC. Here, the diruthenium complex also acts as a redox mediator for the electrocatalytic oxidation of ammonia to dinitrogen at potentials as low as –255 mV vs Fc^0/+ and operates below the ORR potential in alkaline conditions, thus achieving a thermodynamic viability relevant for the future development of DAFCs.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0021021

OSTI ID:: 1835257

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 12 Vol. 13; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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CCDC 1945089: Experimental Crystal Structure Determination J., Trenerry, Michael; M., Wallen, Christian; R., Brown, Tristan https://doi.org/10.5517/ccdc.csd.cc2390t8 The current record is supplemented by this dataset	dataset	January 2021
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Spontaneous N2 formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia

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Spontaneous N₂ formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia