Manipulating the d-Band Center of Ir by Metal-Support Interaction to Optimize the Adsorption for Self-Powered Hydrazine Oxidation-Assisted Hydrogen Generation

Abstract

The hydrazine oxidation-assisted hydrogen generation system significantly expands the applicability of hydrogen production technology. However, the complex intermediate transformations involved in the hydrazine oxidation reaction (HzOR) and hydrogen evolution reaction (HER) desperately need the development of dual-functional catalysts. Manipulating the d-band center of metal catalysts has been identified as one of the most effective approaches to enhance catalytic activity. Herein, Ir nanoparticles (NPs) anchored in B, N-codoped porous carbon (Ir@BNC) were developed and demonstrate excellent performances for both HER and HzOR in an alkaline medium, achieving 10 mA cm⁻² at −25 and 18 mV, respectively. The overall hydrazine splitting (OHzS) electrolyzer reaches 200 mA cm⁻² with a cell voltage of just 0.68 V. The direct liquid N₂H₄/H₂O₂ fuel cell (DHHPFC) assembly with Ir@BNC can achieve a maximum power density of 199.2 mW cm⁻² at room temperature. Furthermore, an H₂ production system using an OHzS device powered by DHHPFC realizes hydrogen production at a stable rate (53.08 mol h⁻¹ m⁻²). In-situ Raman tests and theoretical calculations unravel the metal-support interaction between Ir NPs and B, N-codoped porous carbon, optimizing the electronic structure and regulating the d-band center of Ir, reducing the adsorption energy of H* intermediates and N₂H₄ molecules, thus promoting the reaction processes of HER and HzOR.

Keywords

d-band center / hydrazine oxidation reaction / hydrogen evolution reaction / Ir nanoparticles / metal-support interaction

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2025 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.