Cocktail Effect of 4d/5d Band Twisted High-Entropy Alloys on Carbon Nanotube for Hydrazine Splitting

Herein, multi-walled carbon nanotubes (CNT) embedded with RuPdIrPtAu-high entropy alloys (HEA) via pulsed laser irradiation in liquids are successfully fabricated. The resultant composite synergistically enhances hydrazine oxidation reaction (HzOR)-boosted water electrolysis. Notably, HEA with ≈2-5 nm size, are uniformly distributed across the surface of the CNTs. An optimized HEA/CNT-10 demonstrates exceptional performance in oxygen and hydrogen evolution reactions (OER and HER), depicted by ultralow overpotentials of 30.7 and 330 mV at 10 mA cm^-2, respectively. By replacing OER with HzOR, HEA/CNT-10 needs a lower potential of 0.1 V to accomplish 10 mA cm^-2, as compared to OER (1.56 V vs. RHE). Moreover, the hydrazine splitting electrolyzer desirable a small voltage of 0.242 V to attain 10 mA cm^-2, while maintaining exceptional stability. Experimental and DFT studies validate the cocktail effects and role of multiple metal-sites in HEA/CNT-10, which significantly enhance the efficiency of parallel HER||HzOR processes, highlighting its potential in energy-efficient, hydrogen production. In situ Raman probe indicated the configuration of an acidic environment, monitoring of H₃O⁺, during HER, despite the basic conditions. This is attributed to the dominance of the Heyrovsky step, facilitated by the high catalytic activity of the HEA, coupled with protonation of the CNT surface.