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

作者：Jiachen Li, Yang Li, Yuqiang Ma, Zihang Zhao, Huarong Peng, Tao Zhou, M. Xu, Daidi Fan, Haixia Ma, Jieshan Qiu, Zhengxiao Guo · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.4c17225 · 被引用次数：34 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、CO2 Reduction Techniques and Catalysts、Electrocatalysts for Energy Conversion

High Resolution Image Download MS PowerPoint Slide Electrochemical H 2 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 2 and slow anodic reactions, restricting practical applications of such hybrid systems. Here, we propose a bipolar H 2 production approach, with anodic H 2 generation from the N–N oxidatively coupled dehydrogenation (OCD) of 3,5-diamino-1 H -1,2,4-triazole (DAT), in addition to the cathodic H 2 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 H 2 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 m 3 H 2 ) 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 2 /O 2 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 (Pt 1,n ) optimize the adsorption of the S active sites for H 2 production over the Pt 1,n @VS 2 cathodic catalysts. At the anode, the stepwise dehydrogenation of −NH 2 in DAT and then oxidative coupling of −...