Mitigating Intraphase Catalytic-Domain Transfer via CO Laser for Enhanced Nitrate-to-Ammonia Electroconversion and Zn-Nitrate Battery Behavior.

Developing sustainable energy solutions is critical for addressing the dual challenges of energy demand and environmental impact. In this study, a zinc-nitrate (Zn-NO ) battery system was designed for the simultaneous production of ammonia (NH) via the electrocatalytic NO reduction reaction (NORR) and electricity generation. Continuous wave CO laser irradiation yielded precisely controlled CoFeO@nitrogen-doped carbon (CoFeO@NC) hollow nanocubes from CoFe Prussian blue analogs (CoFe-PBA) as the integral electrocatalyst for NORR in 1.0 M KOH, achieving a remarkable NH production rate of 10.9 mg h cm at -0.47 V versus Reversible Hydrogen Electrode with exceptional stability. In situ and ex situ methods revealed that the CoFeO@NC surface transformed into high-valent Fe/CoOOH active species, optimizing the adsorption energy of NORR (*NO and *NO species) intermediates. Furthermore, density functional theory calculations validated the possible NORR pathway on CoFeO@NC starting with NO conversion to *NO intermediates, followed by reduction to *NO. Subsequent protonation forms the *NH and *NH species, leading to NH formation via final protonation. The Zn-NO battery utilizing the CoFeO@NC cathode exhibits dual functionality by generating electricity with a stable open-circuit voltage of 1.38 V versus Zn/Zn and producing NH. This study highlights the innovative use of CO laser irradiation to transform Prussian blue analogs into cost-effective catalysts with hierarchical structures for NORR-to-NH conversion, positioning the Zn-NO battery as a promising technology for industrial applications.