Understanding the chemistry of the tetravalent actinides is of paramount interest for fundamental f-element science, environmental remediation, and nuclear waste disposal. The tetravalent oxidation state has been well established in metal-organic framework (MOF) synthesis and characterization with zirconium and other transition-metals, but has only recently been extended to the actinide elements. The design tunability and wide range of MOF applications is appealing for the tetravalent actinides as they exhibit challenging chemical properties for synthesis – namely undesirable hydrolysis. Typical de novo synthetic approaches have been lucrative with these materials, but harnessing indirect routes, such as transmetalation and seeding, may prove useful for achieving previously inaccessible actinide MOF products. This work explores the well-known UiO-66 structure, which has already been shown to span various tetravalent metal types – transition-metal, lanthanide, and actinide. We probe experimental conditions to provoke stepwise synthesis such as (i) metal-center exchange in an existing framework with another tetravalent metal type or (ii) isostructural epitaxial growth of the other metal type at the surface – both of which result in mixed-metal frameworks. Evaluation of reaction progress and framework preservation has been determined by powder X-ray diffraction, energy dispersive X-ray spectroscopy, inductively coupled plasma optical emission spectroscopy, and Brunauer-Emmett-Teller analyses.

Indirect synthesis of tetravalent actinide metal-organic frameworks via transformation of the UiO-66 structure

Macromolecular Chemistry: The Second Century

[Author Benefits](https://scimeetings.acs.org/?utm_source=pubs_content_marketing&utm_medium=website&utm_campaign=0320_MCF_NPI_Launch_Spring_Homepage&ref=pubs_content_marketing)

[How to use SciMeetings](https://storage.googleapis.com/dl.morressier.com/acs/SciMeetings-ACSSpring2020-HowToGuide_M3020-Final.pdf)

[Frequently Asked Questions](https://storage.googleapis.com/dl.morressier.com/acs/SciMtng_ACSNMSp2020_FAQ_M3120_Final.pdf)

ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.