The effect of enantioselective chiral covalent organic frameworks and cysteine sacrificial donors on photocatalytic hydrogen evolution

Abstract

Covalent organic frameworks (COFs) have constituted an emerging class of organic photocatalysts showing enormous potential for visible photocatalytic H₂ evolution from water. However, suffering from sluggish reaction kinetics, COFs often cooperate with precious metal co-catalysts for essential proton-reducing capability. Here, we synthesize a chiral β-ketoenamine-linked COF coordinated with 10.51 wt% of atomically dispersed Cu(II) as an electron transfer mediator. The enantioselective combination of the chiral COF-Cu(II) skeleton with L-/D-cysteine sacrificial donors remarkably strengthens the hole extraction kinetics, and in turn, the photoinduced electrons accumulate and rapidly transfer via the coordinated Cu ions. Also, the parallelly stacking sequence of chiral COFs provides the energetically favorable arrangement for the H-adsorbed sites. Thus, without precious metal, the visible photocatalytic H₂ evolution rate reaches as high as 14.72 mmol h⁻¹ g⁻¹ for the enantiomeric mixtures. This study opens up a strategy for optimizing the reaction kinetics and promises the exciting potential of chiral COFs for photocatalysis.

Chiral covalent organic frameworks are demonstrated to enable the docking of sacrificial electron donors via enantioselective combination, thereby improving oxidative half-reaction kinetics and boosting visible photocatalytic H₂ production.