High-Entropy Alloy Nanoflower Array Electrodes with Optimizable Reaction Pathways for Low-Voltage Hydrogen Production at Industrial-Grade Current Density.

Abstract

Developing sufficiently effective non-precious metal catalysts for large-current-density hydrogen production is highly significant but challenging, especially in low-voltage hydrogen production systems. Here, we innovatively report high-entropy alloy nanoflower array (HEANFA) electrodes with optimizable reaction pathways for hydrazine oxidation-assisted hydrogen production at industrial-grade current densities. Atomic-resolution structural analyses confirm the single-phase solid-solution structure of HEANFA. The HEANFA electrodes exhibit the top-level electrocatalytic performance for both the alkaline hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR). Furthermore, the hydrazine oxidation-assisted splitting (OHzS) system assembled with HEANFA as both anode and cathode exhibits a record-breaking performance for hydrogen production. It achieves ultralow working voltages of 0.003, 0.081, 0.260, 0.376, and 0.646 V for current densities of 10, 100, 500, 1 000, and 2 000 mA cm^-2, respectively, and remarkable stability for 300 h, significantly outperforming those of previously reported OHzS systems and other chemicals-assisted hydrogen production systems. Theoretical calculations reveal that extraordinary performance of HEANFA for OHzS is attributed to its abundant high-activity sites and optimizable reaction pathways in HER and HzOR. In particular, HEANFA enables intelligent migration of key intermediates during HzOR, thereby optimizing the reaction pathways and creating high-activity sites, ultimately endowing the extraordinary performance for OHzS.