Ordering Double Perovskite Hydroxides by Kinetically Controlled Aqueous Hydrolysis

被引:19
作者
Neilson, James R. [1 ,2 ]
Kurzman, Joshua A. [1 ,3 ]
Seshadri, Ram [1 ,3 ,4 ]
Morse, Daniel E. [1 ,2 ]
机构
[1] Univ Calif Santa Barbara, Mat Res Lab, Santa Barbara, CA 93106 USA
[2] Univ Calif Santa Barbara, Inst Collaborat Biotechnol, Santa Barbara, CA 93106 USA
[3] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA
[4] Univ Calif Santa Barbara, Dept Mat, Santa Barbara, CA 93106 USA
基金
美国国家科学基金会;
关键词
HYDROTHERMAL PREPARATION; MAGNETIC-PROPERTIES; RIETVELD-ANALYSIS; ZN; MN; CA; MG; MSN(OH)(6); REFINEMENT; NUCLEAR;
D O I
10.1021/ic1025075
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The precipitation of crystals with stoichiometric and ordered arrangements of distinct metal cations often requires carefully designed molecular precursors and/or sufficient activation energy in addition to the necessary mass transport. Here, we study the formation of ordered double perovskite hydroxides, MnSn(OH)(6) and CoSn(OH)(6), of the generic chemical formula, BB'(OH)(6) (no A site), using kinetic control of aqueous hydrolysis from simple metal salt solutions. We find that the precipitation yields ordered compounds only when the B ion is Mn(II) or Co(II), and not when it is any other divalent transition metal ion, or Zn(II). The key step in forming the compounds is the prevention of rapid and uncontrolled hydrolysis of Sn(IV), and this is achieved by a fluoride counteranion. The two compounds, MnSn(OH)(6) and CoSn(OH)(6), are studied by high-resolution synchrotron X-ray diffraction and from the temperature dependence of magnetic behavior. From maximum entropy image restoration of the electron density and from Rietveld analysis, the degree of octahedral distortion and tilting and the small extent of anti-site disorder are determined. From the nonoverlapping electron density, we infer strongly ionic character of bonding. As the first magnetic study of such materials, we report simple paramagnetic behavior with no long-range magnetic order down to 2 K for the Mn(II) compound, while the cobalt compound presents uncompensated antiferromagnetic interactions, attributed to the single-ion anisotropy of octahedral Co(II).
引用
收藏
页码:3003 / 3009
页数:7
相关论文
共 36 条
[1]  
Basciano LC, 1998, CAN MINERAL, V36, P1203
[2]  
Base C.F., 1976, The hydrolysis of cations
[3]   Template-free, low-temperature synthesis of crystalline barium titanate nanoparticles under bio-inspired conditions [J].
Brutchey, Richard L. ;
Morse, Daniel E. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (39) :6564-6566
[4]   HYDROTHERMAL PREPARATION AND LOW-TEMPERATURE MAGNETIC PROPERTIES OF MN(OH)2 [J].
CHRISTENSEN, AN ;
OLLIVIER, G .
SOLID STATE COMMUNICATIONS, 1972, 10 (07) :609-+
[5]   HYDROTHERMAL PREPARATION OF HYDROXY STANNATES - CRYSTAL STRUCTURE OF MNSN(OH)6 [J].
CHRISTENSEN, AN ;
HAZELL, RG .
ACTA CHEMICA SCANDINAVICA, 1969, 23 (04) :1219-+
[6]  
Cotton FA., 1988, Advanced Inorganic Chemistry, V5th ed
[7]   SN-119 NUCLEAR MAGNETIC-RESONANCE STUDIES OF SOME MIXED HALOGENO-COMPLEXES OF TIN(IV) [J].
DILLON, KB ;
MARSHALL, A .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (06) :1245-1247
[8]   Hydroxide ZnSn(OH)6: A promising new photocatalyst for benzene degradation [J].
Fu, Xianliang ;
Wang, Xuxu ;
Ding, Zhengxin ;
Leung, Dennis Y. C. ;
Zhang, Zizhong ;
Long, Jinlin ;
Zhang, Wenxin ;
Li, Zhaohui ;
Fu, Xianzhi .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2009, 91 (1-2) :67-72
[9]   Simonkolleite, Zn5 (OH)8 Cl2 (H2O), a decorated interrupted-sheet structure of the form [Mφ2]4 [J].
Hawthorne, FC ;
Sokolova, E .
CANADIAN MINERALOGIST, 2002, 40 :939-946
[10]  
HENRY M, 1992, STRUCT BOND, V77, P153