Microstructure of NiSO4 Solution:A Combined DFT and EXAFS Study
投稿时间:2018-12-18  修订日期:2018-12-29
DOI:10.12119 / j.yhyj.201902005
中文关键词:  
英文关键词:[NiSO4(H2O)n]0 clusters  Ion pairs  Structure  Energy  Hydration
基金项目:
作者单位E-mail
LIU Hong-yan Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lakes,Chinese Academy of Sciences,Xining,810008,China
Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province,Xining,8100083,China.University of Chinese Academy of Sciences,Beijing,100049,China 
liuhongyan198607@163.com 
ZHU Fa-yan Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lakes,Chinese Academy of Sciences,Xining,810008,China
Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province,Xining,8100083,China.University of Chinese Academy of Sciences,Beijing,100049,China 
 
ZHOU Yong-quan Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lakes,Chinese Academy of Sciences,Xining,810008,China
Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province,Xining,8100083,China.University of Chinese Academy of Sciences,Beijing,100049,China 
 
WANG Guang-guo Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lakes,Chinese Academy of Sciences,Xining,810008,China
Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province,Xining,8100083,China.University of Chinese Academy of Sciences,Beijing,100049,China
Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province,Xining,8100083,China.University of Chinese Academy of Sciences,Beijing,100049,China 
 
FANG Yan Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lakes,Chinese Academy of Sciences,Xining,810008,China
Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province,Xining,8100083,China.University of Chinese Academy of Sciences,Beijing,100049,China 
 
ZHANG Wen-qian Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lakes,Chinese Academy of Sciences,Xining,810008,China
Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province,Xining,8100083,China.University of Chinese Academy of Sciences,Beijing,100049,China 
 
HAN Li Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lakes,Chinese Academy of Sciences,Xining,810008,China  
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中文摘要:
      
英文摘要:
      The microhydration structure of nickel sulfate aqueous solution has been determined via density functional theory(DFT) calculation and extended X-ray absorption fine structure(EXAFS) spectroscopy.The geometric optimization and energy calculation of nickel sulfate hydrated clusters of the molecular formula [NiSO4(H2O)n]0(n=1-12) were determined via DFT using the B3LYP method.Several possible initial structures were considered for clusters of each size to locate the equilibrium geometry.Based on the DFT calculation,the favorable structure of Ni2+ includes the six-coordinated form of [NiSO4(H2O)n]0 clusters.The results of hydration energy calculation suggest that the six-coordinated contact ion pair(CIP) is the stable configuration for small hydration clusters(n≤5),while the solvent-shared ion pair(SSIP) represents the favorable structure for medium hydration clusters(6≤n≤10).The solvent is separated by x water molecules(xSIP,x≥2 is the number of water molecule between Ni2+ and SO2-4) in larger hydration clusters(n≥11).The EXAFS analysis of the NiSO4 aqueous solutions and NiSO4·6H2O solid established that Ni2+ was surrounded by six water molecules tightly forming an octahedral structure in the first hydration shell,and no CIP was found from 0.70 mol/L to 2.22 mol/L(near saturation).The Ni-O distance and coordinated number were 2.040±0.020  and 6.0±1.0,respectively.These results are consistent with the DFT calculations for [NiSO4(H2O)n]0 clusters.DFT and EXAFS are powerful techniques that can be used to enhance the resolution of NiSO4 solution microstructure.
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