Plasmon-enhanced photo(electro)chemical nitrogen fixation under ambient conditions using visible light responsive hybrid hollow Au-Ag2O nanocages
Plasmon-enhanced photo(electro)chemical nitrogen fixation under ambient conditions using visible light responsive hybrid hollow Au-Ag2O nanocages
复制标题
DOI：
10.1016/j.nanoen.2019.103886
复制
发表时间：
2019-09-01
期刊：
影响因子：
17.6
通讯作者：
El-Sayed, Mostafa A.
中科院分区：
文献类型：
--
作者：
Nazemi, Mohammadreza;El-Sayed, Mostafa A.
光（电）催化N-2固定与水在环境条件下提供了一个理想的途径，清洁，可持续和分散的氨生产，并可能作为一个潜在的替代资本和能源密集型哈伯-博世过程。迄今为止，几乎所有用于氮还原反应（NRR）的光催化剂都存在选择性差、由于难以断裂强N=N键而导致活性低、与更有利的析氢反应（HER）竞争以及太阳光谱利用效率低的问题。在这里，一个光（电）化学装置被证明使用混合等离子体半导体作为可见光下的活性光催化剂。利用混合中空Au-Ag 2 O纳米笼在纯水体系中将大气中的N2-转化为NH3，而不使用牺牲试剂。在一个太阳光照下，平均NH3产率为28.2mg·m（-2）·h（-1），太阳能-氨（STA）转化效率为0.017%.在685 nm的单色光源下获得了1.2%的NH3生产的表观量子效率，这是光催化NRR有史以来报道的最高值之一。使用N-15（2）的同位素标记实验证实，供应的N-2气体是系统中NH3形成的唯一来源。这项工作展示了等离子体激元在具有挑战性的多电子固氮中的应用。
Photo(electro)catalytic N-2 fixation with water under ambient conditions offers an ideal pathway for clean, sustainable, and decentralized ammonia production and might serve as a potential alternative to the capital and energy intensive Haber-Bosch process. To date, almost all photocatalysts for nitrogen reduction reaction (NRR) suffer from poor selectivity, low activity due to the difficulty in breaking the strong N=N bond, competition with the more favorable hydrogen evolution reaction (HER), and inefficient utilization of the solar spectrum. Here, a photo(electro)chemical setup is demonstrated using a hybrid plasmonic-semiconductor as an active photocatalyst under visible light. Hybrid hollow Au-Ag2O nanocages are utilized to convert atmospheric N-2 to NH3 in a pure water system without using sacrificial reagents. The average NH3 production rate of 28.2 mg m(-2) h(-1) and the solar-to-ammonia (STA) conversion efficiency of 0.017% are achieved under one sun illumination. The apparent quantum efficiency of 1.2% for NH3 production is obtained with the monochromatic light source at 685 nm, which is among the highest ever-reported values for the photocatalytic NRR. The isotopic labeling experiments using N-15(2) confirms that supplied N-2 gas is the only source of NH3 formation in the system. This work showcases the application of plasmonic photocatalysis in the challenging multi-electron nitrogen fixation.