Tuning Electronic State and Charge Transport in B←N-Containing 2D Polymer Heterostructures with Efficient Photocatalytic Performance

Linear-conjugated polymers (LCPs) are excellent semiconductor photocatalysts. However, its inherent amorphous structures and simple electron transport channels restrict efficient photoexcited charge separation and transfer. Herein, 2D conjugated engineering is employed to design high-crystalline polymer photocatalysts with multichannel charge transport by introducing alkoxyphenyl sidechains. The electronic state structure and electron transport pathways of the LCPs are investigated using experimental and theoretical calculations. Consequently, the 2D B <- N-containing polymers (2DPBN) exhibit excellent photoelectric characteristics, which enable the efficient separation of electron-hole and rapidly transfer photogenerated carriers to the catalyst surface for efficient catalytic reactions. Significantly, the further hydrogen evolution of 2DPBN-4F heterostructures can be achieved by increasing the fluorine content of the backbones. This study highlights that the rational design of LCP photocatalysts is an effective strategy to spur further interest in photofunctional polymer material applications.

Automated summary

In this study, high-crystalline polymer photocatalysts with multichannel charge transport were designed by employing 2D conjugated engineering and introducing alkoxyphenyl sidechains. The electronic state structure and electron transport pathways of the polymers were investigated using experimental and theoretical calculations. The 2D B <- N-containing polymers (2DPBN) exhibited excellent photoelectric characteristics, enabling efficient charge separation and transfer for catalytic reactions. The hydrogen evolution of 2DPBN-4F heterostructures was achieved by increasing the fluorine content of the backbones. This study highlights the importance of rational design in LCP photocatalysts and generates further interest in photofunctional polymer material applications.