Microwave-assisted synthesis of a nanoamorphous (Ni0.8,Fe0.2) oxide oxygen-evolving electrocatalyst containing only “fast” sites

Nickel-iron oxyhydroxides (Ni1-xFexOOH) are non-precious metal electrocatalysts for the oxygen evolution reaction (OER) that have high efficiency in alkaline media. It has been suggested that the layered-double hydroxide (LDH) crystal structure of Ni0.8Fe0.2OOH contains two types of catalytic sites, "fast" Fe sites and "slow" Ni sites, which may limit the overall activity because only 20% of the catalytic surface is highly active. Herein, we report a facile microwave-assisted synthesis route of creating a nanoamorphous nickel-iron oxide electrocatalyst that contains only "fast" catalytic sites. Benchmarking experiments on flat electrodes (roughness factors <1.4) showed that the microwave-assisted, nanoamorphous (Ni-0.8,Fe-0.2) oxide had a low OER overpotential of 286 mV at a current density of 10 mA cm(-2). We measured the kinetic rate constant of the active sites directly with the surface interrogation mode of scanning electrochemical microscopy (SI-SECM). We show that the microwave-assisted, nanoamorphous (Ni-0.8, Fe-0.2) oxide has only one type of catalytic site with an OER kinetic rate constant of 1.9 s(-1) per site. We compared this to a crystalline Ni0.8Fe0.2OOH that was synthesized via electrochemical conditioning of crystalline Ni-0.8:Fe-0.2 oxide, and verified that the Ni0.8Fe0.2OOH contained two types of catalytic sites - "fast" sites with an OER rate constant of 1.3 s(-1) per site and "slow" sites with an OER rate constant of 0.05 s(-1) per site. The percentage of "fast" sites in the crystalline Ni0.8Fe0.2OOH was well matched to the total iron atom content, while 100% of the sites were "fast" in the microwave-assisted, nanoamorphous (Ni-0.8,Fe-0.2) oxide.