Green electrosynthesis of 3,3’-diamino-4,4’-azofurazan energetic materials coupled with energy-efficient hydrogen production over Pt-based catalysts

Abstract

The broad employment of clean hydrogen through water electrolysis is restricted by large voltage requirement and energy consumption because of the sluggish anodic oxygen evolution reaction. Here we demonstrate a novel alternative oxidation reaction of green electrosynthesis of valuable 3,3’-diamino-4,4’-azofurazan energetic materials and coupled with hydrogen production. Such a strategy could greatly decrease the hazard from the traditional synthetic condition of 3,3’-diamino-4,4’-azofurazan and achieve low-cell-voltage hydrogen production on WS2/Pt single-atom/nanoparticle catalyst. The assembled two-electrode electrolyzer could reach 10 and 100 mA cm–2 with ultralow cell voltages of 1.26 and 1.55 V and electricity consumption of only 3.01 and 3.70 kWh per m3 of H2 in contrast of the conventional water electrolysis (~5 kWh per m3). Density functional theory calculations combine with experimental design decipher the synergistic effect in WS2/Pt for promoting Volmer–Tafel kinetic rate during alkaline hydrogen evolution reaction, while the oxidative-coupling of starting materials driven by free radical could be the underlying mechanism during the synthesis of 3,3’-diamino-4,4’-azofurazan. This work provides a promising avenue for the concurrent electrosynthesis of energetic materials and low-energy-consumption hydrogen production.

Seawater electrolysis for fuels and chemicals production: fundamentals, achievements, and perspectives

“…Based on experimental data and theoretical simulations, it was shown that the selectivity of the product can be tuned by controlling the proton–electron transfer reaction network. Recently, our group and co-workers 232 reported a novel oxidative reaction for the green electro-synthesis of DAAzF while simultaneously promoting hydrogen production. This emerging green electro-synthesis process can significantly reduce the environmental hazards caused by traditional industrial methods used to synthesize the DAAzF, and the assembled electrolyzer required only a low cell voltage of 1.55 V to reach 100 mA cm −2 using WS 2 /Pt electrocatalysts.…”

Revealing the Electro-oxidation Mechanism of 5-Aminotetrazole on Nickel-Based Oxides and Synthesizing 5,5′-Azotetrazolate Salts

“…For example, Ma et al proposed replacing the OER with green electrosynthesis of ZT and 3,3′-diamino-4,4′-azofurazan (DAAzF), respectively. This solves the slow four-electron transfer kinetics of OER, producing hydrogen with lower energy consumption (Figure b). , …”

“…This solves the slow four-electron transfer kinetics of OER, producing hydrogen with lower energy consumption (Figure 1b). 12,13 Given that electrochemical organic synthesis involves electrocatalysis and organic chemistry, the complexity of the reaction leads to the absence of research on the mechanism of the electrosynthesis of EMs. In order to promote the application of electrochemicals in the synthesis of energetic materials, it is necessary to explore the mechanism of electrocatalytic energetic materials at a deeper level and design efficient electrocatalysts.…”