Tang Xingrui, Tian Xiuquan, Zhou Li, Yang Fan, He Rong, Zhao Xu, Zhu Wenkun
State Key Laboratory of Environment-friendly Energy Materials, National Co-innovation Center for Nuclear Waste Disposal and Environmental Safety, Sichuan Co-Innovation Center for New Energetic Materials, Nuclear Waste and Environmental Safety Key Laboratory of Defense, School of National Defence Science & Technology, Southwest University of Science and Technology, Mianyang, 621010, Sichuan, China.
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, P. R. China.
Phys Chem Chem Phys. 2022 May 18;24(19):11491-11495. doi: 10.1039/d2cp00340f.
The electrochemical reduction of N into NH under ambient conditions is an attractive topic in the chemical industry, but the chemical inertness of N and the competing hydrogen evolution reaction hamper the activity and selectivity of this reaction. Herein, we connected Ru nanocrystals through a facile annealing process, which constructed intraparticle grain boundaries and stacking faults in the connection regions to enhance the N reduction reaction. The connected Ru nanoparticles exhibited an enhanced yield rate and faradaic efficiency for NH production. At -0.1 V RHE, the connected Ru nanoparticles exhibited a maximum yield rate of 29.3 μg cm h (148.0 μg mg h) for NH production with a faradaic efficiency of 7.0%. Mechanistic study revealed that the promotion of the electrochemical reduction of N over connected Ru nanoparticles could be attributed to the decreased work function and facilitated electron transfer, which originated from the abundant defects in the connection region.
在环境条件下将N电化学还原为NH是化学工业中一个引人关注的课题，但N的化学惰性和竞争性析氢反应阻碍了该反应的活性和选择性。在此，我们通过简便的退火工艺连接Ru纳米晶体，在连接区域构建了颗粒内晶界和堆垛层错，以增强N还原反应。连接的Ru纳米颗粒对NH生成表现出提高的产率和法拉第效率。在-0.1 V（相对于可逆氢电极）时，连接的Ru纳米颗粒对NH生成表现出29.3 μg cm⁻² h⁻¹（148.0 μg mg⁻¹ h⁻¹）的最大产率，法拉第效率为7.0%。机理研究表明，连接的Ru纳米颗粒上N电化学还原的促进可归因于功函数的降低和电子转移的促进，这源于连接区域中丰富的缺陷。
