Unveiling the photoexcitation mechanism of COF-2CN material: From the perspective of molecular structure

Abstract

Covalent organic frameworks (D-A COFs) with electron donor–acceptor structures possess electron transfer channels between the donor and acceptor components, making them potential candidates for applications requiring high photocatalytic activity. In this paper, COF-2CN is selected as a representative material, and computational studies are conducted based on density functional theory (DFT) to gain further insight into its excitation mechanism. First, we used first-principles calculations to determine the molecular structure of COF-2CN. The results reveal that the material has a hexagonal pore shape with a pore size of 25.81 Å, and all atoms in the monolayer structure lie in the same plane. Next, we plotted the density of states (DOS) for COF-2CN and determined that the highest occupied molecular orbital (HOMO) energy level is −0.22 eV. Additionally, we calculated the oscillator strengths for the first 100 excited states and selected 8 states with values greater than 0.2 for further analysis. Subsequently, we analyzed the distribution of electron holes in these excited states and found that, in most cases, the electrons and holes are distributed along the edges of the six-membered rings, with the holes having a broader distribution than the electrons. Finally, we simulated the UV–visible absorption spectrum of COF-2CN, finding that maximum light absorption occurs at a wavelength of 466.1 nm, with an intensity of approximately 454,057 L mol−1 cm−1.