Enhanced photocatalytic performance in seawater of donor-acceptor type conjugated polymers through introduction of alkoxy groups in the side chain.

Abstract

Previous studies have demonstrated that the donor (D)-acceptor (A) structure enables conjugated polymers (CPs) to effectively inhibit charge recombination, reduce exciton binding energy to a minimum, and broaden the light absorption spectrum, ultimately enhancing photocatalytic activity. Besides, side chain engineering is an effective approach to enhance photocatalytic performance by regulating surface chemistry and energy band structure of CPs. Herein, three D-A type CPs, namely TPD-T, TPD-MOT and TPD-DOT, were designed and synthesized using thieno[3,4-c]pyrrole-4,6-dione (TPD) as A units and thiophene with different alkyl/alkoxy groups side chain (as 3-octylthiophene (T), 3-methoxythiophene (MOT) and 3,4-ethylenedioxythiophene (DOT)) as D units, via an atom- and step-economic CH/CH cross-coupling polycondensation. The photocatalytic hydrogen production performance of these polymers driven by visible light was systematically evaluated in pure water and natural seawater. The results show that the hydrogen evolution rates (HERs) of the as-synthesized CPs in pure water and natural seawater significantly increased by 5 and 7 times, respectively, when the number of alkoxy groups on the side chain of polymers increased from 0 to 2. In particular, HERs of three polymers in natural seawater are distinctly better than that in pure water. Further, the steady-state photoluminescence (PL), time-resolved fluorescence decay, and electrochemical impedance spectroscopy (EIS) studies combined with density functional theory (DFT) simulations were carried out to figure out the possible mechanism of the enhanced photocatalytic performance of CPs by side chain engineering. This work indicates that side chain engineering contributes significantly to determine the photocatalytic activity of D-A polymers-based photocatalysts, and could serve as guidelines for organic photocatalysts with highly efficient hydrogen evolution performance.