Highly Durable Compositionally Variant Bifunctional Tetrametallic Ni–Co–Mn–Fe Phosphide Electrocatalysts Synthesized by a Facile Electrodeposition Method for High-Performance Overall Water Splitting

In the recent few decades, the demand for green sources of energy that are clean and sustainable became very essential to reduce the greenhouse and global warming problems. Consequently, there is an increasing demand to identify nonprecious, cheap bifunctional electrocatalysts for water splitting. Herein, nanosheets of different earth-abundant Ni, Co, Mn, and Fe combinations are electrodeposited over commercial Ti mesh and tested for the overall water splitting. The bare Ti mesh requires overpotentials of −486.6 mV at −10 mA cm–2 and 534.5 mV at 10 mA cm–2 for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. However, the electrodeposited catalysts show much higher catalytic activity for both HER and OER with overpotentials of −300 and 279 mV at −10 and 10 mA cm–2, respectively, lowering the overpotential needed to drive the OER by 50%. Nevertheless, to enhance the electrocatalytic performance of the fabricated catalysts, they are phosphidized using different phosphorous precursors. The resulted NiCoMnFe–P catalysts exhibit much lower HER overpotential (−200 mV at −10 mA cm–2), which is 40% lower than that needed by the bare Ti mesh. For the overall water splitting, a cell voltage of 1.71 V is recorded to achieve a current density of 10 mA cm–2. Lastly, the stability test of the overall device reveals very high stability with current retention of 90% over 22 h of continuous electrolysis. Furthermore, the synergy between the metallic components in the absence and presence of P is elucidated using density functional theory calculations, revealing optimized GH* and GH2O* for the HER reaction over the P-top site of the MnFeCoNiP catalyst. In addition, the calculations explain the superiority of the NiCoMnFe catalyst over the NiCoMnFeP counterpart for the OER.