Replacing CC Unit with B←N Unit in Isoelectronic Conjugated Polymers for Enhanced Photocatalytic Hydrogen Evolution

Small. 2023 Sep;19(36):e2302384. doi: 10.1002/smll.202302384. Epub 2023 Apr 28.

Abstract

Three linear isoelectronic conjugated polymers PCC, PBC, and PBN are synthesized by Suzuki-Miyaura polycondensation for photocatalytic hydrogen (H2 ) production from water. PBN presented an excellent photocatalytic hydrogen evolution rate (HER) of 223.5 µmol h-1 (AQY420 = 23.3%) under visible light irradiation, which is 7 times that of PBC and 31 times that of PCC. The enhanced photocatalytic activity of PBN is due to the improved charge separation and transport of photo-induced electrons/holes originating from the lower exciton binding energy (Eb ), longer fluorescence lifetime, and stronger built-in electric field, caused by the introduction of the polar B←N unit into the polymer backbone. Moreover, the extension of the visible light absorption region and the enhancement of surface catalytic ability further increase the activity of PBN. This work reveals the potential of B←N fused structures as building blocks as well as proposes a rational design strategy for achieving high photocatalytic performance.

Keywords: B←N unit; exciton binding energy; isoelectronic conjugated polymers; photocatalysts; photocatalytic hydrogen production.