Affiliation:
1. Center for Molecular Electrocatalysis Pacific Northwest National Laboratory Richland Washington 99352 USA
2. Current address: College of Chemistry Central China Normal University Wuhan Hubei 430079 P. R. China
Abstract
AbstractAmmonia is a promising candidate in the quest for sustainable, clean energy. With its capacity to serve as an energy carrier, the oxidation of ammonia opens avenues for carbon‐neutral approaches to address worldwide growing energy needs. We report the catalytic chemical oxidation of ammonia by an Earth‐abundant transition metal complex, trans‐[LFeII(MeCN)2][PF6]2, where L is a macrocyclic ligand bearing four N‐heterocyclic carbene (NHC) donors. Using triarylaminium radical cations in MeCN, up to 182 turnovers of N2 per Fe were obtained from chemical catalysis with an extremely low loading of the Fe catalyst (0.043 mM, 0.004 mol % catalyst). This chemical catalysis was successfully transitioned to mediated electrocatalysis for the oxidation of ammonia. Molecular electrocatalysis by the Fe catalyst and the mediator (p‐MeOC6H4)3N exhibited a catalytic half‐wave potential (Ecat/2) of 0.18 V vs [Cp2Fe]+/0 in MeCN, and achieved 9.3 turnovers of N2 at an applied potential of 0.20 V vs [Cp2Fe]+/0 at −20 °C in controlled‐potential electrolysis, with a Faradaic efficiency of 75 %. Based on computational results, the catalyst undergoes sequential oxidation and deprotonation steps to form [LFeIV(NH2)2]2+, and thereafter bimetallic coupling to form an N−N bond.
Funder
Energy Frontier Research Centers