Superior methanol electrooxidation performance of (110)-faceted nickel polyhedral nanocrystals

Abstract

We present the synthesis of (110)-faceted nickel polyhedral nanocrystals (NCs) and their characterization as electrocatalysts for the methanol oxidation reaction (MOR). Ni NCs were produced at 180 °C through the reduction in solution of a Ni salt. They were combined with carbon black and Nafion and deposited over glassy carbon to study their electrocatalytic properties. Electrodes based on (110)-faceted Ni NCs displayed a first order reaction with KOH in the concentration range from 0.1 M to 1.0 M. These electrodes were characterized by higher coverages of active species, but lower diffusion coefficients of the species limiting the reaction rate when compared with electrodes prepared from spherical Ni NCs. Overall, electrodes based on faceted Ni NCs displayed excellent performance with very high current densities, up to 61 mA cm⁻², and unprecedented mass activities, up to 2 A mg⁻¹, at 0.6 V vs. Hg/HgO in 1.0 M KOH containing 1.0 M methanol. These electrodes also displayed a notable stability. While they suffered an activity loss of ca. 30% during the first 10 000 s of operation, afterward activity stabilized at very high current densities, ∼35 mA cm⁻², and mass activities, ∼1.2 A mg⁻¹, with only a 0.5% decrease during operation from 20 000 to 30 000 s.