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Xu L, Luo Y, Sun L, et al. Tuning the properties of the metal-organic framework UiO-67-bpy via post-synthetic N-quaternization of pyridine sites. Dalton Trans. 2016;45(20):8614-21doi: 10.1039/c6dt00992a.
Xu, L., Luo, Y., Sun, L., Pu, S., Fang, M., Yuan, R. X., & Du, H. B. (2016). Tuning the properties of the metal-organic framework UiO-67-bpy via post-synthetic N-quaternization of pyridine sites. Dalton transactions (Cambridge, England : 2003), 45(20), 8614-21. https://doi.org/10.1039/c6dt00992a
Xu, Lei, et al. "Tuning the properties of the metal-organic framework UiO-67-bpy via post-synthetic N-quaternization of pyridine sites." Dalton transactions (Cambridge, England : 2003) vol. 45,20 (2016): 8614-21. doi: https://doi.org/10.1039/c6dt00992a
Xu L, Luo Y, Sun L, Pu S, Fang M, Yuan RX, Du HB. Tuning the properties of the metal-organic framework UiO-67-bpy via post-synthetic N-quaternization of pyridine sites. Dalton Trans. 2016 May 28;45(20):8614-21. doi: 10.1039/c6dt00992a. Epub 2016 May 03. PMID: 27140178.
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Dalton Trans. 2016 May 28;45(20):8614-21. doi: 10.1039/c6dt00992a. Epub 2016 May 03.

Tuning the properties of the metal-organic framework UiO-67-bpy via post-synthetic N-quaternization of pyridine sites.

Dalton transactions (Cambridge, England : 2003)

Lei Xu, Yanping Luo, Lin Sun, Shan Pu, Min Fang, Rong-Xing Yuan, Hong-Bin Du

Affiliations

  1. State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China. [email protected].

PMID: 27140178 DOI: 10.1039/c6dt00992a

Abstract

A new UiO-67-type zirconium metal organic framework (MOF) material UiO-67-bpy-Me (bpy = 2,2-bipyridine-4,4'-dicarboxylic acid, Me = methyl) was prepared by N-quaternization of the pyridine sites in UiO-67-bpy. After N-quaternization, the pristine neutral framework turned cationic while its high thermal and chemical stabilities were primarily preserved. Fast and enhanced anionic dye adsorption was observed in UiO-67-bpy-Me. In addition, despite the decrease in surface area and pore volume, UiO-67-bpy-Me exhibited an evident increase in CO2 uptake compared to UiO-67-bpy. The enhancement was ascribed to the strong interactions between CO2 and the N-quaternized framework. More importantly, as the N-quaternization has changed the electronic structure of the organic linker. UiO-67-bpy-Me showed optical absorption up to ca. 800 nm with a large red shift of 450 nm compared to the pristine UiO-67-bpy (ca. 350 nm). The extended optical absorption may lead to more efficiency in light utilization. A proof-of-concept demonstration showed that UiO-67-bpy-Me could more efficiently catalyze methyl-orange degradation under UV-Vis light irradiation than the pristine UiO-67-bpy. These findings demonstrate that N-quaternization could serve as a facile post-synthetic modification method to tune the chemical/physical properties of free pyridyl-containing MOFs.

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