Enhanced photoelectric properties and photocatalytic CO2 conversion by D-A conjugated polymerization
Herein,two anthraquinone-functionalized donor-acceptor(D-A)conjugated polymeric catalysts(AQ-TEA and AQ-TEB),were prepared via Sonogashira cross-coupling of 2,6-dibromoanthraquinone(AQ)with tris(4-ethynylphenyl)amine(TEA)and 1,3,5-triethynylbenzene(TEB),respectively.The chemical structures and morphologies of the catalysts were characterized by FTIR,XPS,XRD and TEM.The optical and electronic properties of two catalysts were investigated by solid UV/Vis diffuse reflectance spectroscopy,steady-state fluorescence spectroscopy,time-resolved fluorescence spectroscopy,and electrochemical characterization.The results indicated that AQ-TEA derived from 2,6-dibromoanthraquinone and tris(4-ethynylphenyl)amine exhibited stronger visible-light absorption and charge-transfer performance.The catalytic performance of two photocatalysts for the photoreduction of CO2 in the presence of H2O was studied.AQ-TEA showed better performance,with a CO production rate of 392μmol/(g·h),which was 1.8 times that of AQ-TEB.Based on the results of experiments and theoretical calculations,we deduced that the strong intramolecular charge transfer(ICT)in the conjugated polymers could promote their light absorption,photoelectric conversion and photocatalytic performance.This work provides a new insight into design and fabrication of active conjugated polymeric catalysts with high photocatalytic efficiency for solar-energy conversion.
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