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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
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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). |
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