Multistep Dissolution of Lamellar Crystals Generates Superthin Amorphous Ni(OH)2 Catalyst for UOR

Abstract

AbstractUrea oxidation reaction (UOR) is an ideal replacement of the conventional anodic oxygen evolution reaction (OER) for efficient hydrogen production due to the favorable thermodynamics. However, the UOR activity is severely limited by the high oxidation potential of Ni‐based catalysts to form Ni3+, which is considered as the active site for UOR. Herein, by using in situ cryoTEM, cryo‐electron tomography, and in situ Raman, combined with theoretical calculations, a multistep dissolution process of nickel molybdate hydrate is reported, whereby NiMoO4·xH2O nanosheets exfoliate from the bulk NiMoO4·H2O nanorods due to the dissolution of Mo species and crystalline water, and further dissolution results in superthin and amorphous nickel (II) hydroxide (ANH) flocculus catalyst. Owing to the superthin and amorphous structure, the ANH catalyst can be oxidized to NiOOH at a much lower potential than conventional Ni(OH)2 and finally exhibits more than an order of magnitude higher current density (640 mA cm−2), 30 times higher mass activity, 27 times higher TOF than those of Ni(OH)2 catalyst. The multistep dissolution mechanism provides an effective methodology for the preparation of highly active amorphous catalysts.