气候变化领域集成服务门户(CCPortal): Covalent grafting of molecular photosensitizer and catalyst on MOF-808: Effect of pore confinement toward visible light-driven CO2reduction in water

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DOI	10.1039/d0ee03643a
	Covalent grafting of molecular photosensitizer and catalyst on MOF-808: Effect of pore confinement toward visible light-driven CO2reduction in water
	Karmakar S.; Barman S.; Rahimi F.A.; Maji T.K.
发表日期	2021
ISSN	17545692
起始页码	2429
结束页码	2440
卷号	14 期号:4
英文摘要	The photocatalytic reduction of CO2 in water using a single integrated system utilizing sunlight is the ultimate goal for artificial photosynthesis. Here, we report the design and multistep synthesis of Zr-MBA-Ru/Re-MOF for photocatalytic CO2 reduction via post-synthetic linker exchange (PSE) followed by metalation on MOF-808. The simultaneous covalent immobilization of the molecular [Ru(bpy)3]2+ photosensitizer and [Re(bpy)CO3Cl] catalyst in the confined space of the MOF resulted in highly efficient CO2-to-CO formation with a maximum production rate of 440 μmol g-1 h-1 in aqueous medium without any sacrificial electron donor (with selectivity >99%, QE = 0.11). In parallel, under sunlight, this assembly also produces 210 μmol g-1 of CO in 6 h in aqueous medium. In addition, a maximum production rate of 180 μmol g-1 h-1 is observed in MeCN/H2O (2 : 1) mixed solvent medium with BNAH and TEOA as the sacrificial electron donor (with CO selectivity 69%, QE = 0.22). The high surface area-based Zr-MOF (MOF-808) is robust and water-tolerant, and its post-synthetically modifiable pore surface allows us to covalently attach the molecular photosensitizer and catalyst in the confined nanospace. Covalent grafting of the [Ru(bpy)3]2+ photosensitizer significantly enhances the lifetime of the photoexcited electrons, and the proximity of the catalytic site shortens the transport distance of charge carriers during the reaction, resulting in an efficient catalytic activity. The reaction intermediates are characterized using in situ diffuse reflectance FT-IR (DRIFT), which is well-supported by DFT calculations, and the catalytic cycle involving the reaction mechanism is established. This journal is © The Royal Society of Chemistry.
英文关键词	Artificial photosynthesis; Carbon dioxide; Carrier mobility; Catalyst activity; Design for testability; Grafting (chemical); Photosensitizers; Reaction intermediates; Rhenium compounds; Ruthenium compounds; Zirconium compounds; Covalent immobilization; Diffuse reflectance; Maximum production rate; Photocatalytic reduction; Photoexcited electrons; Sacrificial electron donors; Transport distances; Visible-light-driven; Catalyst selectivity; carbon dioxide; catalyst; electrochemical method; photochemistry; reduction
语种	英语
来源期刊	Energy & Environmental Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/190694
作者单位	Molecular Materials Laboratory, Chemistry and Physics of Materials Unit, School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research Jakkur, Bangalore, 560064, India
推荐引用方式 GB/T 7714	Karmakar S.,Barman S.,Rahimi F.A.,et al. Covalent grafting of molecular photosensitizer and catalyst on MOF-808: Effect of pore confinement toward visible light-driven CO2reduction in water[J],2021,14(4).
APA	Karmakar S.,Barman S.,Rahimi F.A.,&Maji T.K..(2021).Covalent grafting of molecular photosensitizer and catalyst on MOF-808: Effect of pore confinement toward visible light-driven CO2reduction in water.Energy & Environmental Science,14(4).
MLA	Karmakar S.,et al."Covalent grafting of molecular photosensitizer and catalyst on MOF-808: Effect of pore confinement toward visible light-driven CO2reduction in water".Energy & Environmental Science 14.4(2021).