The consecutive photoinduced electron transfer (ConPET) process of 1,2,3,5-Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) in CO2 photoreduction to achieve powerful reducing species has been disclosed by activating a bis(terpyridine)ruthenium(II) complex bearing a high overpotential...
Coordination-driven metallo-supramolecular assemblies
are potentially
efficient catalysts in photocatalytic CO2 reduction. However,
the relationship between morphology and photocatalytic performance
remains barely explored. In this work, three metallo-supramolecular
assemblies composed of Zn2+ and a flexible tris(terpyridine)
ligand have been prepared for noble metal-free CO2 photoreduction
on the basis of metal–ligand coordination, hydrogen bonding,
and π–π stacking. The three assemblies possess
distinct self-assembled morphologies including spherical particle,
fibrous-like gel, and microrod. It has been found that the fibrous-like
gel exhibits the best catalytic performance in photoreduction of CO2 to CO with a yield of 6.3 mmol g–1 h–1 and 94.7% selectivity over H2 generation.
Photoelectrochemical measurements, photoluminescence quenching experiments,
and UV–vis absorption spectroscopy studies have demonstrated
that the ligand-based electron transfer of the gel is more efficient
compared with the other two assemblies.
Molecular catalysis is of great interest to CO2 photoreduction. Various transition metal complexes have been developed as efficient molecular catalysts. However, it remains a challenge to catalyze CO2 reduction by a small organic molecular photocatalyst, as the accumulation of multiple electrons in a small organic molecule is normally difficult for CO2 reduction. We report herein a small organic molecular catalyst can be used for selective reduction of CO2 to CO under visible light irradiation. The turnover number (TON) of CO formation is found to be 400±26 with near 100% selectivity in DMF/H2O medium. UV‐Vis absorption spectroscopy, density functional theory (DFT) calculations, and spectroelectrochemical studies demonstrate that the organic molecular catalyst is capable of accumulating electrons through a 2e− reduced product which shows good stability and is responsible for interacting with CO2. These findings elucidate an accessible way to develop purely organic molecular catalysts for CO2 reduction by strengthening the electron accumulation.
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