Breaking through the Separation Barrier of Zr(IV) and Hf(IV): Magical Effect of the Bisamide Ligand

Ting Li; Shishun Dong; Zhaowen Chen; Qifeng Wei; Xiulian Ren

doi:10.1021/acs.inorgchem.2c01904

Breaking through the Separation Barrier of Zr(IV) and Hf(IV): Magical Effect of the Bisamide Ligand

Inorg Chem. 2022 Sep 5;61(35):13915-13923. doi: 10.1021/acs.inorgchem.2c01904. Epub 2022 Aug 22.

Authors

Ting Li^{1

2

3}, Shishun Dong^{1

2

3}, Zhaowen Chen^{1

2}, Qifeng Wei^{1

2

3}, Xiulian Ren^{1

2

3}

Affiliations

¹ School of Chemical Engineering and Chemistry, Harbin Institute of Technology, Harbin 150001, China.
² School of Marine Science and Technology, Harbin Institute of Technology, Weihai 264209, China.
³ Shandong Institute of Ship-Building Technology, Institute of Shipping Oil Residue and Oily Sewage Clean Technology, Weihai, Shandong 264209, China.

PMID: 35994610
DOI: 10.1021/acs.inorgchem.2c01904

Abstract

The fundamental safety improvement of the nuclear industry depends on two important elements: Zr(IV) and Hf(IV). However, the elementary knowledge is that separation processes of the two are difficult, so there are few existing methods to meet the requirement. Furthermore, the process is highly contaminated. The development of green and efficient ligands for the separation of Zr(IV) and Hf(IV) is beneficial to the stable development of the nuclear industry. A bisamide ligand D001 was reported for the extraction and separation of Zr(IV) and Hf(IV). D001 utilizes an anionic association mechanism to extract Zr(IV) and Hf(IV) by coordinating amide groups with metals to form complexes H₂ZrCl₆·2 D001 and H₂HfCl₆·2 D001. Using quantum chemical calculations, we illuminate the extraction mechanism of bisamide ligands and the reasons for their better coordination ability than monoamide ligands and carboxylic acid ligands. A process of bisamide extraction and separation of Zr(IV) and Hf(IV) was established, and the thermodynamic parameters of the process were investigated.