Title: Cobalt-based Co$_3$Mo3N/Co$_4$N/Co Metallic Heterostructure as a Highly Active Electrocatalyst for Alkaline Overall Water Splitting

Abstract: Alkaline water electrolysis is considered a commercially viable option for large-scale hydrogen production. However, this process still faces challenges due to the high voltage (>1.65 V at 10 mA cm$^{-2}$) and its limited stability at higher current densities due to the inefficient electron transport kinetics. Herein, a novel cobalt based metallic heterostructure (Co$_3$Mo3N/Co$_4$N/Co/Co) is designed for application for water electrolysis. Operando Raman experiments reveal that the formation of Co$_3$Mo3N/Co$_4$N/Co heterointerface boosts the free water adsorption and dissociation, resulting in a surplus of protons available for subsequent hydrogen production. Furthermore, the altered electronic structure of Co$_3$Mo3N/Co$_4$N/Co heterointerface optimizes the {\Delta}GH of nitrogen atoms at the interface. This synergistic effect between interfacial nitrogen atoms and metal phase cobalt creates highly efficient hydrogen evolution reaction (HER) active sites, thereby enhancing the overall performance. Additionally, the heterostructure exhibits a rapid OH- adsorption rate, coupled with a strong adsorption strength, leading to improved oxygen evolution reaction (OER) performance. Crucially, the metallic heterojunction facilitates fast electron transport, expediting the aforementioned reaction steps and ultimately improving the overall efficiency of water splitting. The water electrolyzer with Co$_3$Mo3N/Co$_4$N/Co/Co as a catalyst exhibits outstanding performance, requiring an impressively low cell voltage of 1.58 V at 10 mA cm$^{-2}$ and maintaining approximately 100% retention over a remarkable 100 h duration at 200 mA cm$^{-2}$. This performance significantly exceeds that of the commercial Pt/C || RuO2 electrolyzer.