Diacetylene-bridged covalent organic framework as crystalline graphdiyne analogue for photocatalytic hydrogen...

Graphdiyne (GDY) alone as a photocatalyst is unsatisfactory because of its low crystallinity, limited regulation of the band gap, weak photogenerated charge separation, etc., and heterojunctioning with other materials is necessary to activate the photocatalytic activity of GDY. Through elaborate design, a diacetylene-rich linker (S2) was prepared and employed to construct a crystalline and structurally well-defined GDY-like covalent organic framework (COF, namely S2-TP COF) which merges the merits of both COF and GDY to boost the photocatalytic hydrogen evolution reaction (HER). By theoretical prediction on the donor-acceptor (D-A) pair, two other monoacetylene-bridged COFs (S1-TP COF and S3-TP COF) were prepared for comparison. Exhibiting enhanced separation and suppressed recombination of photogenerated excitons, Pt-photodeposited S2-TP COF showed a higher HER rate (10.16 mmol g^-1 h^-1) than the other two non-GDY-like COFs (3.71 and 1.13 mmol g^-1 h^-1). A joint experimental-theoretical study suggests that the appropriate D-A structure for photogenerated charge separation and diacetylene motif as the adsorption site are the key reasons for the boosted HER. This work opens a new avenue for the rational design of COFs as GDY mimics for photocatalytic application.