Visible-Light-Driven Photocatalytic CO 2 Reduction to CO/CH 4 Using a Metal-Organic "Soft" Coordination Polymer Gel.
Parul VermaFaruk Ahamed RahimiDebabrata SamantaArup KunduJyotishman DasguptaTapas Kumar MajiPublished in: Angewandte Chemie (International ed. in English) (2022)
The self-assembly of a well-defined and astutely designed, low-molecular weight gelator (LMWG) based linker with a suitable metal ion is a promising method for preparing photocatalytically active coordination polymer gels. Here, we report the design, synthesis, and gelation behaviour of a tetrapodal LMWG based on a porphyrin core connected to four terpyridine units (TPY-POR) through amide linkages. The self-assembly of TPY-POR LMWG with Ru II ions results in a Ru-TPY-POR coordination polymer gel (CPG), with a nanoscroll morphology. Ru-TPY-POR CPG exhibits efficient CO 2 photoreduction to CO (3.5 mmol g -1 h -1 ) with >99 % selectivity in the presence of triethylamine (TEA) as a sacrificial electron donor. Interestingly, in the presence of 1-benzyl-1,4-dihydronicotinamide (BNAH) with TEA as the sacrificial electron donor, the 8e - /8H + photoreduction of CO 2 to CH 4 is realized with >95 % selectivity (6.7 mmol g -1 h -1 ). In CPG, porphyrin acts as a photosensitizer and covalently attached [Ru(TPY) 2 ] 2+ acts as a catalytic center as demonstrated by femtosecond transient absorption (TA) spectroscopy. Further, combining information from the in situ DRIFT spectroscopy and DFT calculation, a possible reaction mechanism for CO 2 reduction to CO and CH 4 was outlined.
Keyphrases
- energy transfer
- visible light
- photodynamic therapy
- dna methylation
- electron transfer
- room temperature
- quantum dots
- high resolution
- single molecule
- solid state
- molecular docking
- metal organic framework
- water soluble
- gene expression
- hyaluronic acid
- health information
- reduced graphene oxide
- mass spectrometry
- cerebral ischemia
- subarachnoid hemorrhage
- gold nanoparticles
- structural basis
- brain injury
- molecular dynamics simulations