卟啉
光催化
催化作用
金属
材料科学
光化学
固氮酶
人工光合作用
吸附
氧化还原
活动中心
氮气
无机化学
化学
固氮
有机化学
作者
Shanshan Shang,Wei Xiong,Chao Yang,Bernt Johannessen,Rugeng Liu,Hsien‐Yi Hsu,Qinfen Gu,Michael K.H. Leung,Jin Shang
出处
期刊:ACS Nano
[American Chemical Society]
日期:2021-05-24
卷期号:15 (6): 9670-9678
被引量:152
标识
DOI:10.1021/acsnano.0c10947
摘要
The rational design of photocatalysts for efficient nitrogen (N2) fixation at ambient conditions is important for revolutionizing ammonia production and quite challenging because the great difficulty lies in the adsorption and activation of the inert N2. Inspired by a biological molecule, chlorophyll, featuring a porphyrin structure as the photosensitizer and enzyme nitrogenase featuring an iron (Fe) atom as a favorable binding site for N2 via π-backbonding, here we developed a porphyrin-based metal–organic framework (PMOF) with Fe as the active center as an artificial photocatalyst for N2 reduction reaction (NRR) under ambient conditions. The PMOF features aluminum (Al) as metal node imparting high stability and Fe incorporated and atomically dispersed by residing at each porphyrin ring promoting the adsorption and the activation of N2, termed Al-PMOF(Fe). Compared with the pristine Al-PMOF, Al-PMOF(Fe) exhibits a substantial enhancement in NH3 yield (635 μg g–1cat.) and production rate (127 μg h–1 g–1cat.) of 82% and 50%, respectively, on par with the best-performing MOF-based NRR catalysts. Three cycles of photocatalytic NRR experimental results corroborate a stable photocatalytic activity of Al-PMOF(Fe). The combined experimental and theoretical results reveal that the Fe–N site in Al-PMOF(Fe) is the active photocatalytic center that can mitigate the difficulty of the rate-determining step in photocatalytic NRR. The possible reaction pathways of NRR on Al-PMOF(Fe) were established. Our study of porphyrin-based MOF for the photocatalytic NRR will provide insight into the rational design of catalysts for artificial photosynthesis.
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