Insights into the new 3d-5f heterometallic quaternary fluorides: Synthesis, crystal structures, spectroscopic properties, and thermodynamic stability

doi:10.1016/j.ica.2018.12.038

CORC > 上海应用物理研究所 > 中国科学院上海应用物理研究所 > 中科院上海应用物理研究所2011-2017年

	Insights into the new 3d-5f heterometallic quaternary fluorides: Synthesis, crystal structures, spectroscopic properties, and thermodynamic stability
	Liu, Q ; Yin, HQ ; Bao, HL ; Yue, ZH ; Diefenbach, K ; Tang, ZF ; Lin, J ; Wang, JQ
刊名	INORGANICA CHIMICA ACTA
	2019
卷号	487 期号:-页码:362—368
关键词	SITU REDUCTION STEP X-RAY-DIFFRACTION MAGNETIC-PROPERTIES THORIUM SALT GROWTH URANIUM(IV) TRANSITION COMPLEXES COFFINITE
ISSN号	0020-1693
DOI	10.1016/j.ica.2018.12.038
文献子类	期刊论文
英文摘要	Two new 3d-5f heterometallic quaternary fluorides, Na3CrTh6F30 and Na4NiTh6F30, have been synthesized hydrothermally from the reactions between ThF4, CrF3 or NiF2, NaF, and HF. Single crystal X-ray diffraction studies revealed that Na3CrTh6F30, and Na4NiTh6F30 adopt dense three-dimensional structures with the space group P (3) over bar c1. Surprisingly, these two compounds are isotypic and exhibit a rather unusual case of aliovalent substitution of the 3d metal centers (Cr-III <--> Ni-II) which is achieved by losing or gaining a Na+ cation in their structures. The valences of Cr-III and Ni-II have been confirmed by corroborating evidences from bond valence sum, UV-vis, and X-ray absorption near edge structure studies. Na3CrTh6F30 and Na4NiTh6F30, exhibit extraordinary thermal stability up to 500 degrees C and to 800 degrees C, respectively, and they retain their original structures in strong acids including 14.9 M HNO3 and aqua regia. First-principle calculations based on density functional theory indicat that the formation enthalpy of Na3CrTh6F30 is -118.945 kJ/mol; suggesting that Na3CrTh6F30 is thermodynamically stable under the simulated condition. This finding helps shed light on the potential products generated from corrosion or during the thorium nuclear fuel cycle.
语种	英语
内容类型	期刊论文
源URL	[http://ir.sinap.ac.cn/handle/331007/31674]
专题	上海应用物理研究所_中科院上海应用物理研究所2011-2017年
作者单位	1.3579 NW Paisley Ct, Beaverton, OR 97006 USA 2.Chinese Acad Sci, Shanghai Inst Appl Phys, 2019 Jia Luo Rd, Shanghai 201800, Peoples R China;
推荐引用方式 GB/T 7714	Liu, Q,Yin, HQ,Bao, HL,et al. Insights into the new 3d-5f heterometallic quaternary fluorides: Synthesis, crystal structures, spectroscopic properties, and thermodynamic stability[J]. INORGANICA CHIMICA ACTA,2019,487(-):362—368.
APA	Liu, Q.,Yin, HQ.,Bao, HL.,Yue, ZH.,Diefenbach, K.,...&Wang, JQ.(2019).Insights into the new 3d-5f heterometallic quaternary fluorides: Synthesis, crystal structures, spectroscopic properties, and thermodynamic stability.INORGANICA CHIMICA ACTA,487(-),362—368.
MLA	Liu, Q,et al."Insights into the new 3d-5f heterometallic quaternary fluorides: Synthesis, crystal structures, spectroscopic properties, and thermodynamic stability".INORGANICA CHIMICA ACTA 487.-(2019):362—368.