Linker engineering in metal-organic frameworks for dark photocatalysis

Dark reactions featuring continuous activity under light off conditions play a critical role in natural photosynthesis. However, most artificial photocatalysts are inactive upon the removal of the light source, and the artificial photocatalysts with dark photocatalysis abilities have been rarely explored. Herein, we report a Ti-based metal-organic framework (MOF), MIL-125, exhibiting the capability of dark photocatalytic hydrogen production. Remarkably, the introduction of different functional groups onto the linkers enables distinctly different activities of the resulting MOFs (MIL-125-X, X = NH2, NO2, Br). Dynamic and thermodynamic investigations indicate that the production and lifetime of the Ti3+ intermediate are the key factors, due to the electron-donating/-withdrawing effect of the functional groups. As far as we know, this is the first report on dark photocatalysis over MOFs, providing new insights into the storage of irradiation energy and demonstrating their great potential in dark photocatalysis due to the great MOF diversity.

Automated summary

Artificial photocatalysts often lose their activity when the light source is removed, and the exploration of artificial photocatalysts with dark photocatalysis abilities is limited. In this study, a Ti-based metal-organic framework (MOF) called MIL-125 was reported, showing the capability of dark photocatalytic hydrogen production. The introduction of different functional groups onto the MOF resulted in distinct activities.