Abstract: Owing to strong Fe-P interaction that differs the electron distribution beneath metal/phosphide interface of Fe-P alloy, the charge transfer of Fe-P alloy has been accelerated during the electrocatalytic oxidation process and improved the efficiency and durability of overall water splitting. In this work, a novel metallurgical technology in combination with smelting reduction and Single Roller Melting Spinning (SRMS) for the purpose of electrochemical overall water splitting where High-phosphorus Oolitic Iron Ore (HPOIO) has been directly used as the main raw material is developed for preparing amorphous Fe-P alloys strips. The rational modulation on the Fe/P ratio can alter the crystal structure and crystallinity of Fe-P alloy, favor electron transfer, and further trap the positively charged H⁺. The obtained FeP electrocatalyst exhibits 436 and 527 mV at 10 mA cm^-1 with Tafel slopes of 102.3 and 77.2 mV dec^-1 for HER and OER in 1.0 mol/L KOH solution, respectively, especially with long-term stability (∼207 h for HER and ∼42 h for OER). Specifically, the DFT calculation displaying structural advantages and componential superiorities exhibited that P in Fe-P amorphous alloy regulated by systematic P addition optimization might increase the energy density in the Fermi level. Furthermore, the phosphorus content brought about high active surface areas, low impedance, and variable reaction paths-caused low reaction energy barriers with the improved amorphicity and absorption and desorption of intermediates, thereby boosting the overall water splitting activity. This study displays a novel strategy to develop Fe-P amorphous alloy for the stable and efficient overall water splitting.

Key words: High-phosphorus, Oolitic Iron Ore, Fe-P alloy, Smelting reduction, Electrocatalysis Overall water splitting