Plasma-Electrocatalytic Nitrogen Reduction for Ammonia Synthesis.

Authors

Tianqi Zhang, Rusen Zhou, Jungmi Hong, Jingyi Luo, Yufei Xue, Qiang Song, Haoxuan Jiang, Yuting Gao, Jieping Fan, Tianyu Li, Shuai Zhang, Jing Sun, Guoping Gao, Dingxin Liu, Tao Shao, Renwu Zhou, Patrick Cullen

Published in

Journal of the American Chemical Society. Jul 07, 2026. Epub Jul 07, 2026.

Abstract

Electrochemical nitrogen reduction under ambient conditions is constrained by the kinetic inertness of N₂ and competition from the hydrogen evolution reaction. Here, we report an integrated plasma-electrolysis membrane-electrode assembly that couples a microstructured nonthermal surface discharge directly to a gas-diffusion cathode, enabling in situ generation and delivery of vibrationally excited N₂, N₂(ν), to the electrocatalytic interface. Among 14 metal catalysts screened, Ag provided the best balance of activity and selectivity, achieving an NH₃ production rate of 7.7 ± 0.8 nmol s^-1 cm^-2 with an electrochemical Faradaic efficiency of 86 ± 14% at -0.54 V versus RHE under atmospheric pressure and room temperature. Plasma/electrolysis on-off controls and ¹⁵N₂ isotope-labeling experiments establish that NH₃ formation requires simultaneous plasma activation and electrochemical polarization and originates from the supplied N₂. Plasma-kinetic modeling indicates strong vibrational excitation in the discharge, with a calculated effective vibrational temperature of approximately 4300 K and 11.8% of N₂ occupying levels (ν = 4-8). Transport modeling further suggests that these comparatively long-lived excited states persist to the membrane-catalyst region. In situ Raman spectroscopy reveals N-N-containing surface intermediates only during coupled operation, while density functional theory shows that vibrational excitation lowers the free-energy requirement for the initial hydrogenation of N₂ to *NNH and shifts the rate-determining step in a catalyst-dependent manner. These findings establish vibrational-state engineering as a strategy for coupling non-equilibrium molecular activation with electrocatalysis for distributed ammonia synthesis under ambient conditions.

PMID:
42412952
Bibliographic data and abstract were imported from PubMed on 08 Jul 2026.

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