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Title: Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks

Abstract

Growing necessity for efficient nuclear waste management is a driving force for development of alternative architectures towards fundamental understanding of mechanisms involved in actinide integration inside extended structures. In this manuscript, metal-organic frameworks (MOFs) were investigated as a model system for engineering radionuclide containing materials through utilization of unprecedented MOF modularity, which cannot be replicated in any other type of materials. Through the implementation of recent synthetic advances in the MOF field, hierarchical complexity of An-materials were built stepwise, which was only feasible due to preparation of the first examples of actinide-based frameworks with “unsaturated” metal nodes. The first successful attempts of solid-state metathesis and metal node extension in An-MOFs are reported, and the results of the former approach revealed drastic differences in chemical behavior of extended structures versus molecular species. Successful utilization of MOF modularity also allowed us to structurally characterize the first example of bimetallic An-An nodes. To the best of our knowledge, through combination of solid-state metathesis, guest incorporation, and capping linker installation, we were able to achieve the highest Th wt% in mono- and bi-actinide frameworks with minimal structural density. Overall, combination of a multistep synthetic approach with homogeneous actinide distribution and moderate solvothermal conditions couldmore » make MOFs an exceptionally powerful tool to address fundamental questions responsible for chemical behavior of An-based extended structures, and therefore, shed light on possible optimization of nuclear waste administration.« less

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
  2. Pacific Northwest National Laboratory, Richland, Washington 99352, United States
  3. College of Engineering and Computing, University of South Carolina, Columbia, South Carolina 29208, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Hierarchical Waste Form Materials (CHWM)
Sponsoring Org.:
USDOE
OSTI Identifier:
1430432
Report Number(s):
PNNL-SA-128941
Journal ID: ISSN 0002-7863; KC0207010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 46
Country of Publication:
United States
Language:
English
Subject:
Nuclear Waste Forms; MOFs; Actinide; hierarchal material; Complexity; modularity; Framework

Citation Formats

Dolgopolova, Ekaterina A., Ejegbavwo, Otega A., Martin, Corey R., Smith, Mark D., Setyawan, Wahyu, Karakalos, Stavros G., Henager, Charles H., zur Loye, Hans-Conrad, and Shustova, Natalia B. Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks. United States: N. p., 2017. Web. doi:10.1021/jacs.7b09496.
Dolgopolova, Ekaterina A., Ejegbavwo, Otega A., Martin, Corey R., Smith, Mark D., Setyawan, Wahyu, Karakalos, Stavros G., Henager, Charles H., zur Loye, Hans-Conrad, & Shustova, Natalia B. Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks. United States. doi:10.1021/jacs.7b09496.
Dolgopolova, Ekaterina A., Ejegbavwo, Otega A., Martin, Corey R., Smith, Mark D., Setyawan, Wahyu, Karakalos, Stavros G., Henager, Charles H., zur Loye, Hans-Conrad, and Shustova, Natalia B. Tue . "Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks". United States. doi:10.1021/jacs.7b09496.
@article{osti_1430432,
title = {Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks},
author = {Dolgopolova, Ekaterina A. and Ejegbavwo, Otega A. and Martin, Corey R. and Smith, Mark D. and Setyawan, Wahyu and Karakalos, Stavros G. and Henager, Charles H. and zur Loye, Hans-Conrad and Shustova, Natalia B.},
abstractNote = {Growing necessity for efficient nuclear waste management is a driving force for development of alternative architectures towards fundamental understanding of mechanisms involved in actinide integration inside extended structures. In this manuscript, metal-organic frameworks (MOFs) were investigated as a model system for engineering radionuclide containing materials through utilization of unprecedented MOF modularity, which cannot be replicated in any other type of materials. Through the implementation of recent synthetic advances in the MOF field, hierarchical complexity of An-materials were built stepwise, which was only feasible due to preparation of the first examples of actinide-based frameworks with “unsaturated” metal nodes. The first successful attempts of solid-state metathesis and metal node extension in An-MOFs are reported, and the results of the former approach revealed drastic differences in chemical behavior of extended structures versus molecular species. Successful utilization of MOF modularity also allowed us to structurally characterize the first example of bimetallic An-An nodes. To the best of our knowledge, through combination of solid-state metathesis, guest incorporation, and capping linker installation, we were able to achieve the highest Th wt% in mono- and bi-actinide frameworks with minimal structural density. Overall, combination of a multistep synthetic approach with homogeneous actinide distribution and moderate solvothermal conditions could make MOFs an exceptionally powerful tool to address fundamental questions responsible for chemical behavior of An-based extended structures, and therefore, shed light on possible optimization of nuclear waste administration.},
doi = {10.1021/jacs.7b09496},
journal = {Journal of the American Chemical Society},
number = 46,
volume = 139,
place = {United States},
year = {Tue Nov 07 00:00:00 EST 2017},
month = {Tue Nov 07 00:00:00 EST 2017}
}