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Atomically Dispersed Mn Synergized With LiBaH3 on MgO Enables Efficient Ammonia Synthesis via an H- Assisted N2
Yanbo Deng1,2, Yaoqi Huang1,3, Yongcheng Jin2
1Low-carbon Technology & Chemical Reaction Engineering Lab, College of Chemical Engineering, Sichuan University, Chengdu, China.
None:
Ammonia is an essential chemical feedstock and a promising hydrogen energy carrier, motivating the development of efficient ammonia synthesis catalysts. However, scaling relations fundamentally limit conventional transition metal-based catalysts, rendering strongly N2-binding metals such as Mn ineffective due to sluggish hydrogenation. Herein, we demonstrate that atomically dispersed Mn (Mn1) anchored on the ternary hydride LiBaH3 (LiBaH3─Mn1) enables efficient ammonia synthesis via an H- ion-assisted N2 dissociation mechanism. The MgO supported LiBaH3─Mn1 catalyst (LiBaH3─Mn1/MgO) exhibits an ammonia synthesis rate two orders of magnitude higher than that of manganese nitride and exceeds the benchmark Cs─Ru/MgO catalyst by a factor of 2.5 at 400°C, representing a state-of-the-art performance among group 4-7 transition metal-based catalysts. Mechanistic investigations reveal that Mn1 serves as the active site for N2 adsorption, while H- ions from LiBaH3 further activate the adsorbed *N2 through a reductive protonation process to form *N2H intermediates. Subsequent N─N bond cleavage of *N2H yields surface nitride (Mn─N) and imide (*NH) species on the LiBaH3─Mn1 surface. This H- ion-assisted N2 dissociation pathway fundamentally overcomes the intrinsic limitations of bulk Mn, transforming it into an efficient metal for ammonia synthesis.
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