A better fundamental understanding of the plasma-catalyst interaction and the reaction mechanism is vital for optimizing the design of catalysts for ammonia synthesis by plasma-catalysis. In this work, we report on a hybrid plasma-enhanced catalytic process for the synthesis of ammonia directly from N₂ and H₂ over transition metal catalysts (M/Al₂O₃, M = Fe, Ni, Cu) at near room temperature (∼35 °C) and atmospheric pressure. Reactions were conducted in a specially designed coaxial dielectric barrier discharge (DBD) plasma reactor using water as a ground electrode, which could cool and maintain the reaction at near-room temperature. The transparency of the water electrode enabled operando optical diagnostics (intensified charge-coupled device (ICCD) imaging and optical emission spectroscopy) of the full plasma discharge area to be conducted without altering the operation of the reactor, as is often needed when using coaxial reactors with opaque ground electrodes. Compared to plasma synthesis of NH₃ without a catalyst, plasma-catalysis significantly enhanced the NH₃ synthesis rate and energy efficiency. The effect of different transition metal catalysts on the physical properties of the discharge is negligible, which suggests that the catalytic effects provided by the chemistry of the catalyst surface are dominant over the physical effects of the catalysts in the plasma-catalytic synthesis of ammonia. The highest NH₃ synthesis rate of 471 μmol g^-1 h^-1 was achieved using Ni/Al₂O₃ as a catalyst with plasma, which is 100% higher than that obtained using plasma only. The presence of a transition metal (e.g., Ni) on the surface of Al₂O₃ provided a more uniform plasma discharge than Al₂O₃ or plasma only, and enhanced the mean electron energy. The mechanism of plasma-catalytic ammonia synthesis has been investigated through operando plasma diagnostics combined with comprehensive characterization of the catalysts using N₂ physisorption measurements, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), NH₃-temperature-programmed desorption (TPD), and N₂-TPD. Four forms of adsorbed NH _x (x = 0, 1, 2, and 3) species were detected on the surfaces of the spent catalysts using XPS. It was found that metal sites and weak acid sites could enhance the production of NH₃ via formation of NH₂ intermediates on the surface.

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