Colloidal Synthesis of Nickel Arsenide Nanocrystals for Electrochemical Water Splitting

We report a detailed study on the first colloidal synthesis of NiAs nanocrystals. By optimizing the synthesis parameters, we were able to obtain trioctylphosphine-capped NiAs nanoplatelets with an average diameter of ∼10 nm and a thickness of ca. 4 nm. We then studied the performance of such NiAs nanocrystals as electrocatalysts for electrochemical water splitting reactions, namely, acidic hydrogen evolution reaction (HER) and alkaline oxygen evolution reaction (OER). These nanocrystals were found to be the most HER active ones among the transition metal arsenides reported to date despite exhibiting less than 40 h of stability under benchmark operative conditions (i.e., −10 mA cmgeo –2). When tested as alkaline OER electrocatalysts, our NiAs nanocrystals behaved as a pre-catalyst and transformed superficially into an active Ni-oxy/hydroxide. As a result, NiAs nanocrystals featured an OER activity higher than that of benchmark Ni0 nanocrystals. Noticeably, the OER performance, in terms of η 10 m A c m g e o − 2 O E R , was retained for up to 60 h of continuous operation. The present study highlights how transition metal arsenides, whose structural features could be successfully controlled through a proper tuning of the synthetic parameters, might represent an emerging class of materials for electrocatalytic applications.