File Download
Links for fulltext
(May Require Subscription)
- Publisher Website: 10.1021/jacs.4c17225
- Scopus: eid_2-s2.0-86000632540
- Find via
Supplementary
-
Citations:
- Scopus: 0
- Appears in Collections:
Article: Electrochemical N–N Oxidatively Coupled Dehydrogenation of 3,5-Diamino-1H-1,2,4-triazole for Value-Added Chemicals and Bipolar Hydrogen Production
Title | Electrochemical 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 Date | 8-Mar-2025 |
Publisher | American 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 Identifier | http://hdl.handle.net/10722/355262 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Li, Jiachen | - |
dc.contributor.author | Li, Yang | - |
dc.contributor.author | Ma, Yuqiang | - |
dc.contributor.author | Zhao, Zihang | - |
dc.contributor.author | Peng, Huarong | - |
dc.contributor.author | Zhou, Tao | - |
dc.contributor.author | Xu, Ming | - |
dc.contributor.author | Fan, Daidi | - |
dc.contributor.author | Ma, Haixia | - |
dc.contributor.author | Qiu, Jieshan | - |
dc.contributor.author | Guo, Zhengxiao | - |
dc.date.accessioned | 2025-04-01T00:35:18Z | - |
dc.date.available | 2025-04-01T00:35:18Z | - |
dc.date.issued | 2025-03-08 | - |
dc.identifier.citation | Journal of the American Chemical Society, 2025, v. 147, n. 11, p. 9505-9518 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://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.language | eng | - |
dc.publisher | American Chemical Society | - |
dc.relation.ispartof | Journal of the American Chemical Society | - |
dc.rights | This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. | - |
dc.title | Electrochemical 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.type | Article | - |
dc.description.nature | published_or_final_version | - |
dc.identifier.doi | 10.1021/jacs.4c17225 | - |
dc.identifier.scopus | eid_2-s2.0-86000632540 | - |
dc.identifier.volume | 147 | - |
dc.identifier.issue | 11 | - |
dc.identifier.spage | 9505 | - |
dc.identifier.epage | 9518 | - |
dc.identifier.eissn | 1520-5126 | - |
dc.identifier.issnl | 0002-7863 | - |