Artificial light harvesting system of CM6@Zn-MOF nanosheets with highly enhanced photoelectric performance

Spectrochim Acta A Mol Biomol Spectrosc. 2025 Jan 15:325:125152. doi: 10.1016/j.saa.2024.125152. Epub 2024 Sep 17.

Abstract

As donors for effective energy transfer, metal-organic frameworks (MOFs) have attracted the attention of many experts in the field of artificial light-harvesting materials. This study introduces a novel two-dimensional Zn-MOF, synthesized using flexible 1,3-phenyldiacetic acid (H2mpda) and rigid 1,3,5-tris(1-imidazolyl)benzene (tib) as organic ligands. Through atomic force microscopy (AFM), we have determined the monolayer thickness of this novel material to be 5 nm. Achieving two-dimensional Zn-MOF nanosheets with large BET surface area was made possible by employing ultrasonic stripping techniques. The fluorescence emission spectrum of Zn-MOF nanosheets overlaps with the UV-vis absorption spectrum of coumarin 6 (CM6), so they can be used as a donor and acceptor for fluorescence resonance energy transfer (FRET) to construct an artificial light-harvesting system (ALHS). Compared with single crystal Zn-MOF, CM6@Zn-MOF(2) has a larger BET surface area (41 m2/g), higher quantum yield (Φfl, 30.56 %), narrower energy gap (Eg, 2.87 eV), and the light-harvesting range extends to the visible green light area. Notably, CM6@Zn-MOF(2) demonstrates a robust photocurrent response, characterized by a photocurrent on/off ratio (Ilight/Idark) of 21, and a maximum photocurrent density that surpasses that of pure Zn-MOF (2.25:1). This study successfully designed a high-performance photoelectric conversion material CM6@Zn-MOF(2), which laid a certain theoretical foundation for new artificial optical acquisition systems and electrochemical material selection.

Keywords: Artificial light-harvesting system; Coumarin 6; Fluorescence resonance energy transfer; Metal–organic frameworks; Photocurrent response.