Solvent-exfoliated D-A π-polymer @ ZnS heterojunction for efficient photocatalytic hydrogen evolution

Abstract

Constructing organic/inorganic soft-hard semiconductor heterojunctions has emerged as a promising strategy to design high-performance photocatalysts. Herein, N-methyl pyrrolidone-assisted solvent exfoliation is employed for the first time to the in-situ construction of benzothidiazole (BT) and bithiophene (TT)-based donor-acceptor (D-A) π-polymeric-inorganic heterojunction (i.e., BT-TT@ZnS) for Pt-free photocatalytic hydrogen production (PHP). Despite that the pristine polymer BT-TT has no photocatalytic activity, the BT-TT@ZnS heterostructure, however, shows a photocatalytic hydrogen evolution rate up to 15.8 mmol g−1 h−1 in the absence of Pt co-catalyst, which is also 10.5 times as high as that of pristine ZnS, and outperforms the majority of the previously reported π-polymers photocatalysts. Systematical studies reveal that BT-TT@ZnS heterostructures simultaneously possess the broadened light absorption and the improved charge separation compared to the single components of BT-TT or ZnS. This work develops a facile and generally applicable strategy to construct π-polymer colloids @ inorganic heterostructure for PHP application.