Electrocatalytic Self-Coupling of N-Heterocyclic Amides for Energy-Efficient Bipolar Hydrogen Production

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🔬研究者:この論文は、電極触媒反応の設計と水素製造効率向上に関する新たな知見を提供する。

🏢実務担当者:水電解装置のエネルギー消費削減と副産物価値向上に応用可能な技術を提案している。

Replacing anodic oxygen evolution reaction with 3,5-diamino-1,2,4-triazole oxidative coupling enables ultra-low-voltage (0.96 V @10 mA cm− 2) dual-electrode H2 production and simultaneous synthesis of energetic 5,5′-diamino-3,3′-azido-1H-1,2,4-triazole (DAAT), achieving 35.8% energy savings. A Pt single-atom/nanoparticle hybrid on NiS2 nanosheets (Pts,n@NiS2@CC) exhibits exceptional alkaline hydrogen evolution reaction performance and stability via optimized H* adsorption. Anodic DAAT formation proceeds via an OH*-mediated N–N coupling pathway, enabling stable (> 300 h @500 mA cm− 2), industrial-scale bipolar H2 production coupled with green DAAT synthesis in an anion-exchange membrane water electrolyzer. Replacing anodic oxygen evolution reaction with 3,5-diamino-1,2,4-triazole oxidative coupling enables ultra-low-voltage (0.96 V @10 mA cm− 2) dual-electrode H2 production and simultaneous synthesis of energetic 5,5′-diamino-3,3′-azido-1H-1,2,4-triazole (DAAT), achieving 35.8% energy savings. A Pt single-atom/nanoparticle hybrid on NiS2 nanosheets (Pts,n@NiS2@CC) exhibits exceptional alkaline hydrogen evolution reaction performance and stability via optimized H* adsorption. Anodic DAAT formation proceeds via an OH*-mediated N–N coupling pathway, enabling stable (> 300 h @500 mA cm− 2), industrial-scale bipolar H2 production coupled with green DAAT synthesis in an anion-exchange membrane water electrolyzer. This study proposes a green electrochemical strategy for addressing the high-energy-barrier oxygen evolution reaction (OER) in traditional overall water splitting. Leveraging the thermodynamic advantages of N–H bond activation/cleavage and N–N coupling processes, the 3,5-diamino-1,2,4-triazole (DAT) oxidative coupling reaction (DATOR) has been introduced to replace the high-energy-barrier oxygen evolution reaction (OER). This substitution enables low-energy-consumption hydrogen production while simultaneously yielding high-value azo energetic materials. Furthermore, to enhance electron and atom economy, the anodic DATOR process allows the hydrogen radicals (H*) generated from amine dehydrogenation to chemically combine via the Tafel process, producing hydrogen gas. By constructing coupling system with Pts,n@NiS2@CC cathode and CuO/CF anode, the operating voltage of the system was significantly reduced (0.96 V@10 mA cm− 2), which was 680 mV more energy efficient than conventional water electrolysis (1.64 V). In situ spectroscopy and theoretical calculations indicate that the anode DATOR generates DAAT through the N–H bond cleavage and N–N coupling path mediated by hydroxyl radicals (OH*), while releasing hydrogen gas. The coupling system has been operating stably for more than 300 h at an industrial-grade current density. This research provides new ideas for dual-electrode hydrogen production and green electrosynthesis of functional materials, with significant energy and economic benefits.

• semanticscholar https://doi.org/10.1007/s40820-025-02025-3first seen 2026-05-15 20:09:23