Boosting CO 2 photoreduction by π-π-induced preassembly between a Cu(I) sensitizer and a pyrene-appended Co(II) catalyst.
Jia-Wei WangZizi LiZhi-Mei LuoYanjun HuangFan MaStefanie GräfeGangfeng OuyangPublished in: Proceedings of the National Academy of Sciences of the United States of America (2023)
The design of a highly efficient system for CO 2 photoreduction fully based on earth-abundant elements presents a challenge, which may be overcome by installing suitable interactions between photosensitizer and catalyst to expedite the intermolecular electron transfer. Herein, we have designed a pyrene-decorated Cu(I) complex with a rare dual emission behavior, aiming at additional π-interaction with a pyrene-appended Co(II) catalyst for visible light-driven CO 2 -to-CO conversion. The results of 1 H NMR titration, time-resolved fluorescence/absorption spectroscopies, quantum chemical simulations, and photocatalytic experiments clearly demonstrate that the dynamic π-π interaction between sensitizer and catalyst is highly advantageous in photocatalysis by accelerating the intermolecular electron transfer rate up to 6.9 × 10 5 s -1 , thus achieving a notable apparent quantum yield of 19% at 425 nm with near-unity selectivity. While comparable to most earth-abundant molecular systems, this value is over three times of the pyrene-free system (6.0%) and far surpassing the benchmarking Ru(II) tris(bipyridine) (0.3%) and Ir(III) tris(2-phenylpyridine) (1.4%) photosensitizers under parallel conditions.
Keyphrases
- visible light
- electron transfer
- highly efficient
- energy transfer
- photodynamic therapy
- molecular dynamics
- quantum dots
- high resolution
- single molecule
- reduced graphene oxide
- monte carlo
- metal organic framework
- diabetic rats
- solid state
- computed tomography
- gold nanoparticles
- ionic liquid
- room temperature
- mass spectrometry
- drug induced
- aqueous solution