《厦门大学学报（自然科学版）》

通过水热法成功合成了两个过渡金属锗磷酸盐化合物Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co,Fe),并采用粉末X射线衍射、单晶X射线衍射、红外光谱分析和热分析方法对样品进行表征.结果表明:这两个过渡金属锗磷酸盐化合物同构,是为数不多的具有二维层状结构的锗磷酸盐; 同时由于Ge元素的d轨道电子数排满,姜-泰勒效应不明显,使得化合物Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co,Fe)结构中由GeO4(OH)2八面体和MⅡO4(OH)2(MⅡ=Co,Fe)八面体通过共棱连接的一维金属链相对较直.

In this paper,the synthetic chemistry of transition metal germanophosphates system has been explored.Two isostructural transition metal germanophosphate compounds Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co,Fe)were successfully synthesized by hydrothermal method.And the compounds were characterized using powder X-ray diffraction,single crystal X-ray diffraction,infrared spectroscopy and thermal analysis methods.Their crystal structures,determined from single crystal data,possessed two-dimensional layered structures built from single chains of edge-sharing MⅡO4(OH)2 and GeO4(OH)2 octahedra,and the single chains were interconnected by HPO4tetrahedra.At the same time,the single chain of edge-sharing MⅡO4(OH)2 and GeO4(OH)2 octahedra was relatively straight compared with other metal phosphates,this may attribute to the weak John-Teller effect of germanium element,for which the d-orbital was full filled with electrons.

引言
1 实验部分
2 结果与讨论
3 结论

图1 化合物1(a)和化合物2(b)的实测PXRD谱图,及Cs[FeGe(OH)2(H0.5PO4)2]的理论计算谱图(c)<br/>Fig.1 Measured PXRD spectra of compounds 1(a)and 2(b), and theoretical calculation PXRD spectrum of Cs[FeGe(OH)2(H0.5PO4)2](c)

图1 化合物1(a)和化合物2(b)的实测PXRD谱图,及Cs[FeGe(OH)2(H0.5PO4)2]的理论计算谱图(c)
Fig.1 Measured PXRD spectra of compounds 1(a)and 2(b), and theoretical calculation PXRD spectrum of Cs[FeGe(OH)2(H0.5PO4)2](c)

表1 化合物1的晶体学数据<br/>Tab.1 Crystal lographic data of compound 1

表1 化合物1的晶体学数据
Tab.1 Crystal lographic data of compound 1

图2 Cs[CoGe(OH)2(H0.5PO4)2]的晶体结构<br/>Fig.2 Crystal structure of Cs[CoGe(OH)2(H0.5PO4)2]

图2 Cs[CoGe(OH)2(H0.5PO4)2]的晶体结构
Fig.2 Crystal structure of Cs[CoGe(OH)2(H0.5PO4)2]

图3 Cs[CoGe(OH)2(H0.5PO4)2]的非对称结构单元中Co、Ge、P的配位环境<br/>Fig.3 Coordination environments of the cobalt,germanium and phosphorus atoms in the asymmetric unit of Cs[CoGe(OH)2(H0.5PO4)2]

图3 Cs[CoGe(OH)2(H0.5PO4)2]的非对称结构单元中Co、Ge、P的配位环境
Fig.3 Coordination environments of the cobalt,germanium and phosphorus atoms in the asymmetric unit of Cs[CoGe(OH)2(H0.5PO4)2]

表2 Cs[CoGe(OH)2(H0.5PO4)2]的原子键价参数<br/>Tab.2 Bond valence parameters of Cs[CoGe(OH)2(H0.5PO4)2]

表2 Cs[CoGe(OH)2(H0.5PO4)2]的原子键价参数
Tab.2 Bond valence parameters of Cs[CoGe(OH)2(H0.5PO4)2]

图4 3种化合物的金属链比较<br/>Fig.4 The comparison of three kinds of metal chains

图4 3种化合物的金属链比较
Fig.4 The comparison of three kinds of metal chains

图5 化合物Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co(a),Fe(b))的FT-IR谱图<br/>Fig.5 FT-IR spectra of Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co(a),Fe(b))

图5 化合物Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co(a),Fe(b))的FT-IR谱图
Fig.5 FT-IR spectra of Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co(a),Fe(b))

图6 Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co(a),Fe(b))在氮气中的TG曲线<br/>Fig.6 TG curves in nitrogen of Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co(a),Fe(b))

图6 Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co(a),Fe(b))在氮气中的TG曲线
Fig.6 TG curves in nitrogen of Cs[MⅡGe(OH)2(H0.5PO4)2](MⅡ=Co(a),Fe(b))

[1] OLSON D H,HAAG W O,LAGO R M.Chemical and physical properties of the ZSM-5 substitional series[J].Journal of Catalysis,1980,61(2):390-396.
[2] CUNDY C S,COX P A.The hydrothermal synthesis of zeolites:history and development from the earliest days to the present time[J].Chemical Reviews,2003,103(3):663-701.
[3] OLSON D H,KOKOTAILO G T,LAWTON S L,et al.Crystal structure and structural related properties of ZSM-5[J].Journal of Physical Chemistry,1981,85(15):2238-2243.
[4] WILSON S T,LOK B M,MESSINA C A,et al.Aluminophosphate molecular sieves:a new class of microporous crystalline inorganic solids[J].Journal of the American Chemical Society,1982,104(4):1146-1147.
[5] CORMA A.From microporous to mesoporous molecular sieve materials and their use in catalysis[J].Chemical Reviews,1997,97(6):2373-2419.
[6] MASPOCH D,RUIZ M D,VECIANA J.Old materials with new tricks:multifunctional open-framework materials[J].Chemical Society Reviews,2007,36(5):770-818.
[7] MOORE P B,SHEN J.An X-ray structural study of cacoxenite,a mineral phosphate[J].Nature,1983,306:356-358.
[8] DAI P S E,PETTY R H,INGRAM C W,et al.Metal substituted aluminophosphate molecular sieves as phenol hydroxylation catalysts[J].Applied Catalysis A:General,1996; 143(1):101-110.
[9] LIN S S,WENG H S.Liquid-phase oxidation of cyclo-hexane using CoAPO-5 as the catalyst[J].Applied Cataly-sis A:General,1993,105(2):289-308.
[10] AMINE K,YASUDA H,YAMACHI M.Olivine LiCoPO4 as 4.8 V electrode material for lithium batteries[J].Electrochemical and Solid State Letters,2000,3(4):178-179.
[11] YAMADA A,CHUNG S C,HINOKUMA K.Optimized LiFePO4 for lithium battery cathodes[J].Journal of the Electrochemical Society,2001,148(3):A224-A229.
[12] FENG J K,XIA H,LAI M O,et al.NASICON-structured LiGe2(PO4)3 with improved cyclability for high performance lithium batteries[J].The Journal of Physical Chemistry C,2009,113(47):20514-20520.
[13] KOSEVA I,NIKOLOV V,PESHEV P.Effect of germanium doping on the morphology of flux grown Nb:KTiOPO4 single crystals[J].Journal of Alloys and Compounds,2003,353(1/2):L1-L4.
[14] LI J M,KE Y X,ZHANG Y G,et al.((DABCO)·ZnGe(HPO4)3:the first zinco-germanophosphate with a unique asymmetric cage[J].Journal of the American Chemical Society,2000,122(25):6110-6111.
[15] TEREBILENKO K V,SLOBODYANIK N S,OGO-RODNYK I V,et al.Crystallization of MIGe2(PO4)3(MI=Na,K,Ag)from molten phosphate media[J].Crystal Research and Technology,2014,49(4):227-231.
[16] HUANG Y X,LIU B,WEN L,et al.Structural assembly from phosphate to germanophosphate by applying germanate as a binder[J].Inorganic Chemistry,2013,52:9169-9171.
[17] SHELDRICK G M.A short history of SHELX[J].Acta Crystallographica Section A,2008,64:112-122.
[18] SHELDRICK G M.Crystal structure refinement with SHELXL[J].Acta Crystallographica Section C:Structural Chemistry,2015,71:3-8.
[19] MI J X,BORRMANN H,ZHANG H,et al.Synthesis,magnetism,and crystal structure of Li2Fe[(PO4)(HPO4)] and its hydrogen position refinement[J].Zeitschrift fur Anorganische und Allgemeine Chemie,2004,630:1632-1636.
[20] HUANG Y X,ZHANG X,HUANG X,et al.Two isotypic transition metal germanophosphates M4Ⅱ(H2O)4Ge(OH)2(HPO4)2(PO4)2(MⅡ=Fe,Co):synthesis,structure,Mossbauer spectroscopy,and magnetic properties[J].Inorganic Chemistry,2012,51(5):3316-3323.
[21] BROWN I D,ALTERMATT D.Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database[J].Acta Crystallographica Section B:Structural Science,1985,41:244-247.
[22] LIGHTFOOT P,CHEETHAM A K,SLEIGHT A W.Hydrothermal synthesis and crystal structure of a new layered phosphate,K2CO3(P2O7)2·2H2O[J].Journal of Solid State Chemistry,1990,85(2):275-282.

备注

引言

1 实验部分

2 结果与讨论

3 结论

学报简介

备注

引言

1 实验部分

2 结果与讨论

3 结 论

学报简介

3 结论