Issue 16, 2024

Role of Lewis acid/base anchor atoms in catalyst regeneration: a comprehensive study on biomimetic EP3Fe nitrogenases

Abstract

In the quest for sustainable ammonia synthesis routes, biomimetic complexes have been intensively studied. Here we focus on the Peter's group Fe-nitrogenase catalyst with EPPP scorpionate ligands, and explore the effect of anchor atom selection (B, Al, Ga, N and P) and the impact of chloro substitution on the phenyl rings on nitrogen fixation. The reaction profiles of complexes with Lewis basic anchor atoms exhibited energy-demanding reduction steps, with more exergonic protonation steps compared to the smoother reaction profiles observed for catalysts with Lewis acid anchor atoms, also implying that catalyst regeneration is especially challenging for catalysts with Lewis basic anchor atoms. The binding affinities of N2 and H2 to the complexes suggest that the autocatalytic hydrogen evolution reaction (HER), which ultimately leads to consumption of reactants and catalyst deactivation, is likely to become more prevalent for heavier anchor atoms and be more significant for Lewis basic anchor atom complexes. Out of the studied complexes, boron showed the smoothest reaction profile and the smallest affinity for H2, which supports its superiour role as an anchor atom in accordance with experimental data.

Graphical abstract: Role of Lewis acid/base anchor atoms in catalyst regeneration: a comprehensive study on biomimetic EP3Fe nitrogenases

Supplementary files

Article information

Article type
Paper
Submitted
01 Febr. 2024
Accepted
07 Marts 2024
First published
11 Marts 2024

Phys. Chem. Chem. Phys., 2024,26, 12520-12529

Role of Lewis acid/base anchor atoms in catalyst regeneration: a comprehensive study on biomimetic EP3Fe nitrogenases

J. Kfoury and J. Oláh, Phys. Chem. Chem. Phys., 2024, 26, 12520 DOI: 10.1039/D4CP00483C

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