Aerobic Photodegradation of Pyrene-Based Metal-Organic Framework NU-1000 to Terephthalic Acid

Author(s)
Wenyi Zeng, Tristan T.Y. Tan, Youven Benseghir, Michael R. Reithofer, Jia Min Chin, Jason Y.C. Lim
Abstract

NU-1000, a pyrene-containing benchmark metal-organic framework (MOF), is well-known for its utility and potential across a wide range of applications. Although the extended π-systems in NU-1000 confer favorable properties for diverse photochemical applications, they also increase the susceptibility of the MOF to photodegradation. However, the photostability of NU-1000 has yet to be systematically studied and remains poorly understood. Herein, we report that in the presence of oxygen, water, and light of appropriate energy, extensive oxidation of the pyrene linkers of NU-1000 can occur to yield terephthalic acid as the major decomposition product. Through extensive mechanistic studies, we show that the open framework structure of NU-1000 greatly facilitates linker oxidation, with more than 25-fold greater linker decomposition from the MOF within 3 h of photoirradiation compared to a homogeneous solution of the linker, brought about by rapid generation of pyrene-centred holes. By determining the specific conditions under which the MOF remains stable, our findings offer not just valuable strategies for preserving the integrity of NU-1000 for controlled applications but also reveal its ability to decompose into benign products under ambient light and oxygen, which could provide an eco-friendly route for avoiding environmental accumulation of MOF materials for various applications.

Organisation(s)
Department of Inorganic Chemistry, Department of Functional Materials and Catalysis
External organisation(s)
Agency for Science, Technology and Research A*STAR, National University of Singapore (NUS)
Journal
Chemistry of Materials
Volume
37
Pages
3531-3541
No. of pages
11
ISSN
0897-4756
DOI
https://doi.org/10.1021/acs.chemmater.5c00520
Publication date
2025
Peer reviewed
Yes
Austrian Fields of Science 2012
104011 Materials chemistry, 205004 Functional materials
ASJC Scopus subject areas
General Chemistry, General Chemical Engineering, Materials Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/52e447c9-7557-4fbc-b26e-27152ab230af