Lattice Oxygen Leaching Induced Amorphous/Crystalline Heterostructured MnO x /Ni 9 S 8 Nanoarrays Construction for Efficient Methanol Electro‐Reforming at Large Current Density

ABSTRACT Electrocatalytic reforming of methanol into highvalue‐added formate is regarded as a promising alternative to alkaline oxygen evolution reaction with sluggish reaction kinetics. However, it holds huge challenges for the practical application of conventional nickel‐based catalysts under industrial‐level current density. Herein, the amorphous/crystalline heterostructured oxygen vacancy‐rich MnO x /Ni 9 S 8 nanoarrays induced by lattice oxygen leaching are constructed for efficient methanol oxidation reaction (MOR). The MnO x /Ni 9 S 8 exhibits an extremely low potential of 1.55 V (vs. RHE) at an industrial‐grade current density of 1 A cm −2 , together with a 96.76% Faradaic efficiency of formate. A membrane‐free MnO x /Ni 9 S 8 || MnO x /Ni 9 S 8 cell for MOR || HER delivers electrocatalytic activity that requires merely a cell voltage of 1.57 V for 100 mA cm −2 , yielding a 95.66% Faradaic efficiency while maintaining continuous electrolysis for 150 h. The systematic studies manifest that the coupling of amorphous/crystalline interfaces and numerous oxygen vacancies not only modulates electron distribution and accelerates the generation of active sites Ni III ‐OOH, but also enhances the adsorption capacity for OH − and methanol, thereby boosting overall performance. This work demonstrates an efficient lattice oxygen leaching‐induced strategy for industrial‐level methanol electro‐reforming to formate, providing a new prototype for valorization of biomass into high‐value chemicals and production of hydrogen energy.