Gel-Derived Amorphous Bismuth-Nickel Alloy Promotes Electrocatalytic Nitrogen Fixation via Optimizing Nitrogen Adsorption and Activation.

To achieve the electrochemical nitrogen reduction reaction (NRR) for efficient and sustainable NH production, catalysts should exhibit high selectivity and activity with optimal adsorption energy. Herein we developed a three-dimensional (3D) amorphous BiNi alloy toward a significantly enhanced NRR compared with its crystalline and metal counterparts. Ni alloying enables the chemisorption of nitrogen and the lower free-energy change for the *NNH formation, and the 3D alloy electrocatalyst exhibits high catalytic activity for NH production with a yield rate of 17.5 μg h  mg and Faradaic efficiency of 13.8 %. The enhanced electron transfer and increased electrochemical surface area were revealed in the interconnected porous scaffold, affording it sufficiently efficient and stable activity for potential practical applications. This work offers new insights into optimizing the adsorption energy of reactants and intermediates combined with tuning the crystallinity of NRR electrocatalysts.