Synergistically enhanced performance of transition-metal doped Ni2P for supercapacitance and overall water splitting

Abstract

Cost-effective and readily available catalysts applicable for electrochemical conversion technologies are highly desired. Herein, we report the synthesis of dithiophosphonate complexes of the type [Ni{S₂P(OH)(4-CH₃OC₆H₄)}₂] (1), [Co{S₂P(OC₄H₉)(4-CH₃OC₆H₄)}₃] (2) and [Fe{S₂P(OH)(4-CH₃OC₆H₄)}₃] (3) and employed them to prepare Ni₂P, Co-Ni₂P and Fe-Ni₂P nanoparticles. Ni₂P was formed by a facile hot injection method by decomposing complex 1 in tri-octylphosphine oxide/tri-n-octylphosphine at 300 °C. The prepared Ni₂P was doped with Co and Fe employing complexes 2 and 3, respectively, under similar experimental conditions. Doping Ni₂P with Co and Fe demonstrated synergistic improvement of Ni₂P performance as an electrocatalyst in supercapcitance, hydrogen evololution and oxygen evolution reactions in alkaline medium. Cobalt doping improved the Ni₂P charge storage capacity with a supercapacitance of 864 F g⁻¹ at 1 A g⁻¹ current density. Fe doped Ni₂P recorded the lowest overpotential of 259 mV to achieve a current density of 10 mA cm⁻² and a Tafel slope of 80 mV dec⁻¹ for OER, better than the undoped Ni₂P and the benchmark IrO₂. Likewise, Fe-doped Ni₂P electrode required the lowest overpotential of 68 mV with a Tafel slope of 110 mV dec⁻¹ to attain the same current density for HER. All catalysts showed excellent stability in supercapacitance and overall water splitting reactions, indicating their practical use in energy conversion technologies.