Tuning the Optoelectronic Properties of Hybrid Functionalized MIL-125-NH2 for Photocatalytic Hydrogen Evolution

Metal-organic frameworks (MOFs) constructed with mixed ligands have shown great promise in the generation of materials with improved sorption, optical, and electronic properties. With an experimental, spectroscopic, and computational approach, herein, we investigated how the incorporation of different functionalized ligands within the structure of MIL-125-NH2 affects its performance in photocatalytic water reduction. We found that multiligand incorporation within the MOF structure has an impact on the light absorption spectrum and the electronic structure. These combined modifications improve the photocatalytic performance of MIL-125-NH2, thereby increasing the rate of hydrogen evolution reaction. Of the four nanoparticle/MOF photocatalytic systems tested, we showed that the Pt/MIL-125-NH2/(OH)(2) system (Pt nanoparticle plus MIL-125-NH2 with amino and dihydroxyl functionalized ligands) outperforms its counterpart Pt/MIL-12S-NH2 system, attributed to the enhanced p-pi conjugation between the lone pairs of O atoms and their aromatic ligands resulting in a red-shifted absorption spectrum and greater spatial distribution of electron density.

Automated summary

Metal-organic frameworks (MOFs) constructed with mixed ligands show great promise in improving materials' properties, with the incorporation of different functionalized ligands within the MOF structure impacting its performance in photocatalytic water reduction. The presence of multiligand incorporation modifies the light absorption spectrum and electronic structure, enhancing the photocatalytic performance and hydrogen evolution rate. Among the tested nanoparticle/MOF photocatalytic systems, the Pt/MIL-125-NH2/(OH)(2) system outperforms its counterpart due to enhanced p-pi conjugation and red-shifted absorption spectrum.