Enhancing Nitrate Reduction to Ammonia Through Crystal Phase Engineering: Unveiling the Hydrogen Bonding Effect in -FeOOH Electrocatalysis

Crystal phase engineering has emerged as a powerful tool for tailoring the electrocatalytic performance, yet its impact on nitrate reduction to ammonia (NRA) remains largely uncharted territory. Herein, density functional theory (DFT) calculations are performed to unravel the influence of the crystal phase of FeOOH on the adsorption behavior of *NO3. Inspiringly, FeOOH samples with four distinct crystal phases (delta, gamma, alpha, and beta) are successfully synthesized and deployed as electrocatalysts for NRA. Remarkably, among all FeOOH samples, delta-FeOOH demonstrates the superior NRA performance, achieving a NH3 Faradic efficiency (FENH3$\rm{FE} _ {\rm{NH_3}}$) of 90.2% at -1.0 V versus reversible hydrogen electrode (RHE) and a NH3 yield rate (YieldNH3$\rm{Yield} _ {\rm{NH_3}}$) of 5.73 mg h-1 cm-2 at -1.2 V. In-depth experiments and theoretical calculations unveil the existence of hydrogen bonding interaction between delta-FeOOH and *NOx, which not only enhances the adsorption of *NOx but also disrupts the linear relationships between the free energy of *NO3 adsorption and various parameters, including limiting potential, d-band center (epsilon d) and transferred charge from FeOOH to *NO3, ultimately contributing to the exceptional NRA performance. Crystal phase engineering is proposed to improve the performance of FeOOH toward electrochemical nitrate reduction to ammonia (NRA), with delta-FeOOH exhibiting superior NRA performance. Mechanistic studies unveil that hydrogen bonding interaction formed between delta-FeOOH and *NOx intermediates results in enhanced adsorption of *NOx, and breaks the linear scaling relationship. image