Boosting Hydrogen Evolution by Methanol Oxidation Reaction on Ni-Based Electrocatalysts: From Fundamental Electrochemistry to Perspectives

Hydrogen production via electrocatalytic water splitting is hampered by the slow kinetics of the anodic oxygen evolution reaction (OER). To address this limitation, the electrochemical hydrogen evolution reaction (HER) can be boosted with the more favorable oxidation of small organic molecules ideally driven by renewable energies, producing valuable chemicals. In this context, coupling hydrogen production with the methanol oxidation reaction (MOR) with simultaneous formate production has garnered significant interest. Such a cost-effective electrocatalytic process, meeting the growing demand for energy storage and fuel production, requires developing cheap and efficient electrocatalysts. Given the knowledge gap between precious and nonprecious metal electrocatalysts, exemplified by nickel and its derived compounds, this review focuses on MOR from fundamental electrochemistry, materials design and synthesis, and activity-composition/structure relations. Despite significant advances, we still face formidable challenges in deciphering the intricate catalytic mechanism, elevating the activity and selectivity to new heights, and pioneering the development of scalable prototypes.