Linker engineering in metal–organic frameworks for dark photocatalysis. Issue 22 (24th May 2022)

• Record Type: Journal Article
• Authors: Pan, Yating; Wang, Jingxue; Chen, Shengyi; Yang, Weijie; Ding, Chunmei; Waseem, Amir; Jiang, Hai-Long
• Is Part Of: Chemical science. Volume 13:Issue 22(2022)
• Page Start: 6696
• Page End: 6703
• Publication Date: 2022-05-24
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1sc06785k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : A Ti-based MOF with long-lived Ti 3+ can achieve dark photocatalysis. The different groups on the organic linker modulate electron storage ability and the lifetime of Ti 3+, significantly regulating dark photocatalytic activity in H2 production. Abstract : 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 Ti 3+ 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.