GFP Chromophore Integrated Conjugated Microporous Polymers toward Bioinspired Photocatalytic CO2 Reduction to CO

The development of highly active, durable, and low-cost metal-free catalysts for the photocatalytic CO2 reduction reaction (CO2RR) is an efficient and environmentally friendly solution to address significant problems like global warming and high energy demand. In the present study, we have demonstrated the design and synthesis of a donor-acceptor based conjugated microporous polymer (CMP), TPA-GFP, by integrating an electron donor, tris(4-ethynylphenyl)amine (TPA), with a green fluorescent protein chromophore analogue (Z)-4-(2-hydroxy-3,5-diiodobenzylidene)-1-(4-iodophenyl)-2-methyl-1H-imidazol-5(4H)-one (o-HBDI-I3) (GFP). In comparison to nondonor 1,3,5-triethynylbenzene (TEB) based TEB-GFP CMP, photocatalytic CO2 reduction using donor-acceptor based TPA-GFP CMP displays a 3-fold increment of CO production yield with a maximum CO yield of 1666 mu mol g(-1) at 12 h. Further, the CO selectivity increases significantly from a mere 54% in TEB-GFP to an impressive 95% in TPA-GFP. The impressive CO2 reduction efficiency and selectivity for TPA-GFP can be attributed to the efficient light-harvesting capability and facile charge separation and migration through donor-acceptor building units of the CMP. The mechanistic aspect of the photocatalytic CO2 reduction process is explored using in situ DRIFTS and DFT calculation, and a plausible photocatalytic mechanism is proposed.