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Article: Electrochemical N–N Oxidatively Coupled Dehydrogenation of 3,5-Diamino-1H-1,2,4-triazole for Value-Added Chemicals and Bipolar Hydrogen Production

TitleElectrochemical N–N Oxidatively Coupled Dehydrogenation of 3,5-Diamino-1<i>H</i>-1,2,4-triazole for Value-Added Chemicals and Bipolar Hydrogen Production
Authors
Issue Date8-Mar-2025
PublisherAmerican Chemical Society
Citation
Journal of the American Chemical Society, 2025, v. 147, n. 11, p. 9505-9518 How to Cite?
Abstract

Electrochemical H2 production from water favors low-voltage molecular oxidation to replace the oxygen evolution reaction as an energy-saving and value-added approach. However, there exists a mismatch between the high demand for H2 and slow anodic reactions, restricting practical applications of such hybrid systems. Here, we propose a bipolar H2 production approach, with anodic H2 generation from the N–N oxidatively coupled dehydrogenation (OCD) of 3,5-diamino-1H-1,2,4-triazole (DAT), in addition to the cathodic H2 generation. The system requires relatively low oxidation potentials of 0.872 and 1.108 V vs RHE to reach 10 and 500 mA cm–2, respectively. The bipolar H2 production in an H-type electrolyzer requires only 0.946 and 1.129 V to deliver 10 and 100 mA cm–2, respectively, with the electricity consumption (1.3 kWh per m3 H2) reduced by 68%, compared with conventional water splitting. Moreover, the process is highly appealing due to the absence of traditional hazardous synthetic conditions of azo compounds at the anode and crossover/mixing of H2/O2 in the electrolyzer. A flow-type electrolyzer operates stably at 500 mA cm–2 for 300 h. Mechanistic studies reveal that the Pt single atom and nanoparticle (Pt1,n) optimize the adsorption of the S active sites for H2 production over the Pt1,n@VS2 cathodic catalysts. At the anode, the stepwise dehydrogenation of −NH2 in DAT and then oxidative coupling of −N–N– predominantly form azo compounds while generating H2. The present report paves a new way for atom-economical bipolar H2 production from N–N oxidative coupling of aminotriazole and green electrosynthesis of value-added azo chemicals.


Persistent Identifierhttp://hdl.handle.net/10722/355262
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489

 

DC FieldValueLanguage
dc.contributor.authorLi, Jiachen-
dc.contributor.authorLi, Yang-
dc.contributor.authorMa, Yuqiang-
dc.contributor.authorZhao, Zihang-
dc.contributor.authorPeng, Huarong-
dc.contributor.authorZhou, Tao-
dc.contributor.authorXu, Ming-
dc.contributor.authorFan, Daidi-
dc.contributor.authorMa, Haixia-
dc.contributor.authorQiu, Jieshan-
dc.contributor.authorGuo, Zhengxiao-
dc.date.accessioned2025-04-01T00:35:18Z-
dc.date.available2025-04-01T00:35:18Z-
dc.date.issued2025-03-08-
dc.identifier.citationJournal of the American Chemical Society, 2025, v. 147, n. 11, p. 9505-9518-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/355262-
dc.description.abstract<p>Electrochemical H<sub>2</sub> production from water favors low-voltage molecular oxidation to replace the oxygen evolution reaction as an energy-saving and value-added approach. However, there exists a mismatch between the high demand for H<sub>2</sub> and slow anodic reactions, restricting practical applications of such hybrid systems. Here, we propose a bipolar H<sub>2</sub> production approach, with anodic H<sub>2</sub> generation from the N–N oxidatively coupled dehydrogenation (OCD) of 3,5-diamino-1<em>H</em>-1,2,4-triazole (DAT), in addition to the cathodic H<sub>2</sub> generation. The system requires relatively low oxidation potentials of 0.872 and 1.108 V vs RHE to reach 10 and 500 mA cm<sup>–2</sup>, respectively. The bipolar H<sub>2</sub> production in an H-type electrolyzer requires only 0.946 and 1.129 V to deliver 10 and 100 mA cm<sup>–2</sup>, respectively, with the electricity consumption (1.3 kWh per m<sup>3</sup> H<sub>2</sub>) reduced by 68%, compared with conventional water splitting. Moreover, the process is highly appealing due to the absence of traditional hazardous synthetic conditions of azo compounds at the anode and crossover/mixing of H<sub>2</sub>/O<sub>2</sub> in the electrolyzer. A flow-type electrolyzer operates stably at 500 mA cm<sup>–2</sup> for 300 h. Mechanistic studies reveal that the Pt single atom and nanoparticle (Pt<sub>1,n</sub>) optimize the adsorption of the S active sites for H<sub>2</sub> production over the Pt<sub>1,n</sub>@VS<sub>2</sub> cathodic catalysts. At the anode, the stepwise dehydrogenation of −NH<sub>2</sub> in DAT and then oxidative coupling of −N–N– predominantly form azo compounds while generating H<sub>2</sub>. The present report paves a new way for atom-economical bipolar H<sub>2</sub> production from N–N oxidative coupling of aminotriazole and green electrosynthesis of value-added azo chemicals.</p>-
dc.languageeng-
dc.publisherAmerican Chemical Society-
dc.relation.ispartofJournal of the American Chemical Society-
dc.rightsThis work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.-
dc.titleElectrochemical N–N Oxidatively Coupled Dehydrogenation of 3,5-Diamino-1<i>H</i>-1,2,4-triazole for Value-Added Chemicals and Bipolar Hydrogen Production-
dc.typeArticle-
dc.description.naturepublished_or_final_version-
dc.identifier.doi10.1021/jacs.4c17225-
dc.identifier.scopuseid_2-s2.0-86000632540-
dc.identifier.volume147-
dc.identifier.issue11-
dc.identifier.spage9505-
dc.identifier.epage9518-
dc.identifier.eissn1520-5126-
dc.identifier.issnl0002-7863-

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