A Biomimetic Twisting Strategy Enables Efficient Electrocatalytic Oxidation of Energy-Dense Hydrazine Hydrate on...

Electrocatalytic hydrazine oxidation holds great promise for enabling fuel cell-powered transportation since hydrazine hydrate (N₂H₄·H₂O) has the highest energy density of all liquid, CO₂-free fuels (3.45 kWh/L), and the highest fuel cell voltage (1.56 V vs O₂). Inspired by the ruffling of catalytic centers in oxidative enzymes, we designed a twisted single-atom nanozyme comprising twisted FeN₂₊₂C₄₊₄ sites, enabling high accessibility of N₂H₄ and OH^- reactants. Experimental evidence shows that this nanozyme catalyst achieves the lowest oxidation overpotential of all Fe-N-C materials, both in the lab and in direct hydrazine fuel cells, with an open-circuit voltage of 0.95 V, unprecedented for an Fe-based anode. The structure of the catalytic site is elucidated through a combination of electrochemistry, ⁵⁷Fe Mössbauer spectroscopy, high-resolution transmission electron microscopy, and X-ray absorption spectroscopy with crystal field multiplet simulations and fits of the pre-edge features, as well as density functional theory calculations and theoretical simulations of X-ray absorption near edge structure. The experimental and theoretical methods reveal that twisting the active site also shifts its oxidation potential positively and improves N₂ bubble removal while limiting ammonia production to less than 10 ppm. This work demonstrates the potential of active site twisting to enhance the oxidation of energy-rich and liquid substrates, representing a crucial step toward building a sustainable society.