Nickel Phosphide: The Effect of Phosphorus Content on the Activity and Stability toward Oxygen Evolution Reaction in Alkaline Medium

In this work a systematic study of the effect of the metal to phosphorus ratio in Ni-P nanoparticles on their catalytic activity with respect to the OER is reported. To this end, nickel phosphide nanoparticles are synthesized through two different synthesis routes, one involving in-situ phosphidation and one involving ex-situ phosphidation. In-situ phosphidation is performed via two steps route in a one-pot synthesis, in which Ni nanoparticles are formed at 220 °C, but not isolated, and then transformed to phase-pure either Ni12P5 or Ni2P nanocrystallites. In the second synthesis method (ex-situ phosphidation), nickel nanoparticles with an excess amount of trioctylphosphine (TOP) as a capping agent are synthesized and separated from the solution, then subsequently annealed in three different atmospheres, leading to the formation of three types of NixPy viz. NixPy-H2/Ar, NixPy-Ar, and NixPy-air. NixPy-air nanoparticles shows the best electrocatalytic activity among the annealed nanoparticles in Ar and H2/Ar but lower than Ni12P5 nanoparticles. However, NixPy-air shows very high stability in comparison with other synthesized nanoparticles. Moreover, the effect of the adventitious and spiked Fe in the electrolyte is studied on the electrocatalytic activity of all synthesized nanoparticles.