4.8 Article

Influence of Linker Identity on the Photochemistry of Uranyl-Organic Frameworks

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume -, Issue -, Pages -

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.3c06897

Keywords

uranyl; photochemistry; metal-organicframework; photocatalysis

Ask authors/readers for more resources

This study investigated the impact of linker identity and photoexcitation on the photocatalytic performance of uranyl-based MOFs. By analyzing the structural and photochemical properties of three uranyl-based MOFs, the study showed that the photophysical properties of linkers can be used to predict the photocatalytic behavior of uranyl-containing MOFs.
While uranyl-based metal-organic frameworks (MOFs) boast impressive photocatalytic abilities, significant questions remain regarding their excitation pathways and methods to fine-tune their performance due to the lack of information regarding heterogeneous uranyl catalysis. Herein, we investigated how linker identity and photoexcitation impact uranyl photocatalysis when the uranyl coordination environment remains constant. Toward this end, we prepared three uranyl-based MOFs (NU-1301, NU-1307, and ZnTCPP-U2) and then examined the structural and photochemical properties of each through X-ray diffraction, X-ray absorption, and photoluminescence. We then correlated our observations to the photocatalytic performance for fluorination of cyclooctane. The excitation profile from NU-1301 and NU-1307 exhibited spin-forbidden linker transitions and uranyl vibronic progressions, with uranyl excitation and emission being most dominant in NU-1301. Consequently, NU-1301 was a more active photocatalyst than NU-1307. In contrast, the excitation profile from ZnTCPP-U2 contained transitions associated with the porphyrin linker exclusively. Photocatalytic activity from ZnTCPP-U2 significantly underperformed in comparison to that of the other two MOFs. These data suggest that linkers' photophysical properties can be used to predict the photocatalytic behavior of uranyl-containing MOFs.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.8
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

No Data Available
No Data Available