Zhang Jihua, Liu Yi, Li Jianming, Jin Xu, Li Yapeng, Qian Qizhu, Wang Yixuan, El-Harairy Ahmed, Li Ziyun, Zhu Yin, Zhang Huaikun, Cheng Mingyu, Zeng Suyuan, Zhang Genqiang
Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Education University, Guiyang 550018, China.
Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, China.
ACS Appl Mater Interfaces. 2021 Jan 27;13(3):3881-3890. doi: 10.1021/acsami.0c18684. Epub 2021 Jan 19.
Designing highly active transition-metal-based electrocatalysts for energy-saving electrochemical hydrogen evolution coupled with hydrazine oxidation possesses more economic prospects. However, the lack of bifunctional electrocatalysts and the absence of intrinsic structure-property relationship research consisting of adsorption configurations and dehydrogenation behavior of NH molecules still hinder the development. Now, a V-doped NiN nanosheet self-supported on Ni foam (V-NiN NS) is reported, which presents excellent bifunctional electrocatalytic performance toward both hydrazine oxidation reaction (HzOR) and hydrogen evolution reaction (HER). The resultant V-NiN NS achieves an ultralow working potential of 2 mV and a small overpotential of 70 mV at 10 mA cm in alkaline solution for HzOR and HER, respectively. Density functional theory calculations reveal that the vanadium substitution could effectively modulate the electronic structure of NiN, therefore facilitating the adsorption/desorption behavior of H* for HER, as well as boosting the dehydrogenation kinetics for HzOR.
设计用于节能型电化学析氢与肼氧化耦合的高活性过渡金属基电催化剂具有更大的经济前景。然而，缺乏双功能电催化剂以及缺乏由NH分子的吸附构型和脱氢行为组成的内在结构-性能关系研究仍然阻碍着该领域的发展。现在，报道了一种自支撑在泡沫镍上的V掺杂NiN纳米片（V-NiN NS），它对肼氧化反应（HzOR）和析氢反应（HER）均表现出优异的双功能电催化性能。所得的V-NiN NS在碱性溶液中对HzOR和HER分别在10 mA cm时实现了2 mV的超低工作电位和70 mV的小过电位。密度泛函理论计算表明，钒取代可以有效地调节NiN的电子结构，从而促进HER中H*的吸附/解吸行为，并加快HzOR的脱氢动力学。
