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Title: Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

Abstract

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. We overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. Furthermore, these compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest void volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [2];  [2];  [2];  [2];  [3];  [2];  [2];  [2];  [2];  [2];  [3]; ORCiD logo [4];  [2];  [5];  [2]
  1. Soochow Univ., Jiangsu (China). Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions; Nanjing Univ. of Science and Technology (China). School of Environment and Biological Engineering
  2. Soochow Univ., Jiangsu (China). Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions
  3. Chinese Academy of Sciences (CAS), Beijing (China). Shanghai Inst. of Applied Physics and Key Lab. of Nuclear Radiation and Nuclear Energy Technology
  4. Soochow Univ., Jiangsu (China). Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions; IBM Thomas J. Watson Research Center, Yorktown Heights, NY (United States). Computational Biology Center; Columbia Univ., New York, NY (United States). Dept. of Chemistry
  5. Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Florida State Univ., Tallahassee, FL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1389275
Grant/Contract Number:  
SC0016568
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal-organic frameworks; solid-state chemistry

Citation Formats

Zheng, Tao, Yang, Zaixing, Gui, Daxiang, Liu, Zhiyong, Wang, Xiangxiang, Dai, Xing, Liu, Shengtang, Zhang, Linjuan, Gao, Yang, Chen, Lanhua, Sheng, Daopeng, Wang, Yanlong, Diwu, Juan, Wang, Jianqiang, Zhou, Ruhong, Chai, Zhifang, Albrecht-Schmitt, Thomas E., and Wang, Shuao. Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system. United States: N. p., 2017. Web. doi:10.1038/ncomms15369.
Zheng, Tao, Yang, Zaixing, Gui, Daxiang, Liu, Zhiyong, Wang, Xiangxiang, Dai, Xing, Liu, Shengtang, Zhang, Linjuan, Gao, Yang, Chen, Lanhua, Sheng, Daopeng, Wang, Yanlong, Diwu, Juan, Wang, Jianqiang, Zhou, Ruhong, Chai, Zhifang, Albrecht-Schmitt, Thomas E., & Wang, Shuao. Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system. United States. doi:10.1038/ncomms15369.
Zheng, Tao, Yang, Zaixing, Gui, Daxiang, Liu, Zhiyong, Wang, Xiangxiang, Dai, Xing, Liu, Shengtang, Zhang, Linjuan, Gao, Yang, Chen, Lanhua, Sheng, Daopeng, Wang, Yanlong, Diwu, Juan, Wang, Jianqiang, Zhou, Ruhong, Chai, Zhifang, Albrecht-Schmitt, Thomas E., and Wang, Shuao. Tue . "Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system". United States. doi:10.1038/ncomms15369. https://www.osti.gov/servlets/purl/1389275.
@article{osti_1389275,
title = {Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system},
author = {Zheng, Tao and Yang, Zaixing and Gui, Daxiang and Liu, Zhiyong and Wang, Xiangxiang and Dai, Xing and Liu, Shengtang and Zhang, Linjuan and Gao, Yang and Chen, Lanhua and Sheng, Daopeng and Wang, Yanlong and Diwu, Juan and Wang, Jianqiang and Zhou, Ruhong and Chai, Zhifang and Albrecht-Schmitt, Thomas E. and Wang, Shuao},
abstractNote = {Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. We overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. Furthermore, these compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest void volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.},
doi = {10.1038/ncomms15369},
journal = {Nature Communications},
issn = {2041-1723},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {5}
}

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