Photochromic radical states in 3D covalent organic frameworks with zyg topology for enhanced photocatalysis

ABSTRACT

Covalent-organic frameworks (COFs) with photoinduced donor-acceptor (D-A) radical pairs show enhanced photocatalytic activity in principle. However, achieving long-lived charge separation in COFs proves challenging due to the rapid charge recombination. Here, we develop a novel strategy by combining [6 + 4] nodes to construct zyg-type 3D COFs, first reported in COF chemistry. This structure type exhibits a fused Olympic-rings-like shape, which provides a platform for stabilizing the photoinduced D-A radical pairs. The zyg-type COFs containing catalytically active moieties such as triphenylamine and phenothiazine (PTZ) show superior photocatalytic production rates of hydrogen peroxide (H ₂O ₂). Significantly, the photochromic radical states of these COFs show up to 400% enhancement in photocatalytic activity compared to the parent states, achieving a remarkable H ₂O ₂ synthesis rate of 3324 μmol g ⁻¹ h ⁻¹, which makes the PTZ-COF one of the best crystalline porous photocatalysts in H ₂O ₂ production. This work will shed light on the synthesis of efficient 3D COF photocatalysts built on topologies that can facilitate photogenerating D-A radical pairs for enhanced photocatalysis.

Abstract

Three-dimensional donor-acceptor covalent organic frameworks (COFs) with zyg topology featuring Olympic rings-shaped pores were constructed, showing metastable photoinduced charge-separated states which significantly enhanced the photocatalytic synthesis of hydrogen peroxide.