Manipulating wettability of catalytic surface for improving ammonia production from electrochemical nitrogen reduction.

ABSTRACT

An electrochemical nitrogen reduction reaction (ENRR) is considered a promising alternative for the traditional Haber-Bosch process. In this study, we present a method for improving the ENRR by controlling the wettability of the catalyst surface, suppressing the hydrogen evolution reaction (HER) while facilitating N2 adsorption. Reduced-graphene oxide (rGO) with a hydrophobic surface property and a contact angle (C.A.) of 59° was synthesized through a high-density atmospheric plasma deposition. Two other hydrophilic and superhydrophobic surfaces with a C.A. of 15° and 150° were developed through additional argon plasma and heat treatment of as-deposited rGO, respectively. The ENRR results showed that the ammonia yield and Faradaic efficiency tended to increase with increasing hydrophobicity. Electrochemical measurements reveal that superhydrophobic rGO achieves a higher Faradaic efficiency (5.73 %) at -0.1 V (vs RHE) and a higher NH3 yield (9.77 µg h-1 cm-2) at -0.4 V (vs RHE) in a 0.1 M KOH electrolyte. In addition, the computational fluid dynamics simulation confirmed that the amount of time the N2 gas remains on the surface could increase by improving the hydrophobicity of the catalytic surface. This study inspires the development of the rGO electrocatalyst through surface wettability modification for boosting ammonia electrosynthesis.