Facile Carbothermal Synthesis of Metal Phosphides-Based Multifunctional Electrocatalysts via Polyaniline Doped with Phosphoric Acid

Transition metal phosphides (TMPs) and their composites are promising non-platinum electrocatalysts for hydrogen evolution (HER), oxygen evolution (OER), and oxygen reduction (ORR) reactions. But traditional methods to obtain these electrocatalysts are usually multi-step and include the participation of hazardous phosphorus compounds during phosphidation. Here, the possibility of using a polyaniline doped with phosphoric acid (PANI∙H 3 PO 4 )—as a source of C, N and P simultaneously - to obtain composites based on N,P-doped carbon and nano- and/or submicron TMP particles as HER, OER and ORR electrocatalysts is demonstrated. The pyrolysis of PANI∙H 3 PO 4 together with Co, Ni, Mo, or Fe salt allows the formation of such composite electrocatalysts by the carbon thermal reduction route. Regardless of the pH of the electrolyte, the MoP-based electrocatalyst is characterized in HER by the smallest Tafel slope and overpotential of hydrogen evolution and also exhibits high stability during long-term operation. At the same time, other composites are multifunctional electrocatalysts possessing activity not only in HER, but also in OER and ORR. The proposed approach can be a starting point for a simple, universal in choice of d-metal, and environmentally attractive preparation of multifunctional TMP-based electrocatalysts with further improvement of their performance.