Nickel-based catalysts for electrolytic decomposition of ammonia towards hydrogen production

Nickel is an attractive metal for electrochemical applications because it is abundant, cheap, chemically resilient, and catalytically active towards many reactions. Nickel-based materials (metallic nickel, its alloys, oxides, hydroxides, and composites) have been also considered as promising electrocatalysts for ammonia oxidation. The electrolysis of ammonia aqueous solution results in evolution of gaseous hydrogen and nitrogen. Up to date studies showed that metallic Ni and Ni (hydro)oxides are not catalytically active unless they are electrochemically converted to NiOOH at ~1.3 V vs. RHE. Then, dehydrogenation of NH₃ begins with electron coupled proton transfer to NiOOH resulting in a would-be reversible reduction of the latter to Ni(OH)₂. Unlike the water electrolysis process, in which solely oxygen is obtained at the anode, during ammonia electrooxidation apart from release of N₂, many undesired oxygenated nitrogen moieties may also turn up. These products appear after at least partial dehydrogenation of ammonia. Studies on NiOOH activity have been conducted for systems containing various modifiers, e.g., Cu, Co, S, P, however, their particular role in catalytic activity has not yet been elucidated. Nowadays research is being conducted in the direction of increasing the activity, selectivity, and stability of NiOOH. In this review, the electroactivity of Ni is analyzed and discussed in accordance with its oxidation states along with the ammonia oxidation mechanism. The main research problems to be solved and challenges for the future industrial use of ammonia are presented.