Manipulating dehydrogenation kinetics through dual-doping Co<sub>3</sub>N electrode enables highly efficient hydrazine oxidation assisting self-powered H<sub>2</sub> production.

Liu, Yi; Zhang, Jihua; Li, Yapeng; Qian, Qizhu; Li, Ziyun; Zhu, Yin; Zhang, Genqiang · Nat Commun · 2020

basic_science · Level V

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Abstract

Replacing sluggish oxygen evolution reaction (OER) with hydrazine oxidation reaction (HzOR) to produce hydrogen has been considered as a more energy-efficient strategy than water splitting. However, the relatively high cell voltage in two-electrode system and the required external electric power hinder its scalable applications, especially in mobile devices. Herein, we report a bifunctional P, W co-doped Co<sub>3</sub>N nanowire array electrode with remarkable catalytic activity towards both HzOR (-55 mV at 10 mA cm<sup>-2</sup>) and hydrogen evolution reaction (HER, -41 mV at 10 mA cm<sup>-2</sup>). Inspiringly, a record low cell voltage of 28 mV is required to achieve 10 mA cm<sup>-2</sup> in two-electrode system. DFT calculations decipher that the doping optimized H* adsorption/desorption and dehydrogenation kinetics could be the underlying mechanism. Importantly, a self-powered H<sub>2</sub> production system by integrating a direct hydrazine fuel cell with a hydrazine splitting electrolyzer can achieve a decent rate of 1.25 mmol h<sup>-1</sup> at room temperature.