开放骨架磷酸铁的合成与性质

doi:10.7503/cjcu20131247

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (3): 449.doi: 10.7503/cjcu20131247

• 研究论文: 无机化学 • 上一篇下一篇

开放骨架磷酸铁的合成与性质

王艳艳¹, 张铮², 孙延俊¹, 李激扬¹()

1. 吉林大学化学学院, 无机合成与制备化学国家重点实验室, 长春 130012
2. Chemical Reaction Engineering Group, Institute of Technology and Management, University of Groningen, Groningen 9747AG, The Netherlands

收稿日期:2013-12-19 出版日期:2014-03-10 发布日期:2019-08-01
作者简介:联系人简介: 李激扬, 女, 博士, 教授, 博士生导师, 主要从事无机合成化学研究. E-mail: lijiyang@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 21271081)和国家“九七三”计划项目(批准号: 2011CB808703)资助

Synthesis and Characterization of a New Open-framework Iron Phosphate^†

WANG Yanyan¹, ZHANG Zheng², SUN Yanjun¹, LI Jiyang^1,^*()

1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
2. Chemical Reaction Engineering Group, Institute of Technology and Management, University of Groningen, Groningen 9747AG, The Netherlands

Received:2013-12-19 Online:2014-03-10 Published:2019-08-01
Contact: LI Jiyang E-mail:lijiyang@jlu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21271081) and the State Basic Research Project of China(No.2011CB808703)

摘要/Abstract

摘要：

通过使用二丙烯基三胺为结构导向剂, 在水热体系中合成出一例具有新型三维开放骨架结构的磷酸铁化合物JU94( $2 H 3 O$ [Fe₂P₂O₈(OH)₂]). 单晶X射线衍射分析结果显示, 该化合物结晶在单斜晶系P2₁/c空间群, 晶胞参数a=0.97566(5) nm, b=0.98560(5) nm, c=1.24514(5) nm, β=129.651(3)°, V=0.92189(8) nm³. 该化合物的骨架结构是由FeO₆八面体和PO₄四面体连接构成, 以四核铁簇作为结构构筑单元. JU94沿[101], [ $1 ˉ$ 01], [010]和[111]方向含有扭曲八元环孔道, 水分子分布于孔道中. 穆斯堡尔谱研究结果表明, 该结构具有2个晶体学独立的正三价铁离子. 磁性研究结果表明, 该物质具有反铁磁性.

关键词: 磷酸铁, 开放骨架, 水热合成, 反铁磁性

Abstract:

Synthesis of novel iron phosphates has gained much attention due to their structure diversity and unique magnetic property. In this work, a new iron phosphate JU94( $2 H 3 O$ [Fe₂P₂O₈(OH)₂]) with novel three-dimensional open framework has been hydrothermally synthesized using dipropylenetriamine as the structure-directing agent(SDA). Its structure was determined by single-crystal X-ray diffraction. It crystallizes in monoclinics pace group, P2₁/c, with a=0.97566(5) nm, b=0.98560(5) nm, c=1.24514(5) nm, β=129.651(3)°, V=0.92189(8) nm³. The framework structure is made of tetranuclear iron-oxygen clusters as building unit formed by connection of FeO₆ and PO₄ polyhedra, which contains intersecting 8-ring channels along the [101], [ $1 ¯$ 01], [010] and [111] directions. Water molecules are occluded in the free space of channels. Mössbauer analysis shows that there are two types of Fe atoms in the framework, and they are both trivalent. Magnetic measurement shows anti-ferromagnetic ordering of JU94 at room temperature.

Key words: Iron phosphate, Open-framework, Hydrothermal synthesis, Anti-ferromagnetic property

中图分类号:

O614

TrendMD:

王艳艳, 张铮, 孙延俊, 李激扬. 开放骨架磷酸铁的合成与性质. 高等学校化学学报, 2014, 35(3): 449.

WANG Yanyan, ZHANG Zheng, SUN Yanjun, LI Jiyang. Synthesis and Characterization of a New Open-framework Iron Phosphate^†. Chem. J. Chinese Universities, 2014, 35(3): 449.

图/表 9

Table 1 Crystal data and structure refinement for JU94*

Empirical formula	Fe₂P₂ $O 1 2$ H₈
Formula weight	373.70
Temperature/K	293(2)
Wavelength/nm	0.071073
Crystal system, space group	Monoclinic, P2₁/c
a/nm	0.97566(5)
b/nm	0.98560(5)
c/nm	1.24514(5)
β/(°)	129.651(3)
V/nm³	0.92189(8)
Z, calculated density/(Mg·m^-3)	4, 2.693
Absorption coefficient/mm^-1	3.556
F(000)	744
Crystal size	0.15 mm×0.12 mm×0.10 mm
θ range for data collection/(°)	2.71—28.31
Limiting indices	-10≤h≤3
	-13≤k≤11
	-16≤l≤16
Reflections collected/unique	6615/2283(R_int=0.0606)
Completeness to θ=28.31	100.0%
Max. and min. transmission	0.7175 and 0.6176
Refinement method	Full-matrix least-squares on F²
Data/restraints/parameters	2283/0/151
Goodness-of-fit on F²	1.068
Final R indices[I>2σ(I)]	R₁=0.0338, wR₂=0.0965
R indices(all data)	R₁=0.0372, wR₂=0.0987
Largest diff. peak and hole/(e·nm^-3)	1204, -721

Table 1 Crystal data and structure refinement for JU94*

Empirical formula	Fe₂P₂ $O 1 2$ H₈
Formula weight	373.70
Temperature/K	293(2)
Wavelength/nm	0.071073
Crystal system, space group	Monoclinic, P2₁/c
a/nm	0.97566(5)
b/nm	0.98560(5)
c/nm	1.24514(5)
β/(°)	129.651(3)
V/nm³	0.92189(8)
Z, calculated density/(Mg·m^-3)	4, 2.693
Absorption coefficient/mm^-1	3.556
F(000)	744
Crystal size	0.15 mm×0.12 mm×0.10 mm
θ range for data collection/(°)	2.71—28.31
Limiting indices	-10≤h≤3
	-13≤k≤11
	-16≤l≤16
Reflections collected/unique	6615/2283(R_int=0.0606)
Completeness to θ=28.31	100.0%
Max. and min. transmission	0.7175 and 0.6176
Refinement method	Full-matrix least-squares on F²
Data/restraints/parameters	2283/0/151
Goodness-of-fit on F²	1.068
Final R indices[I>2σ(I)]	R₁=0.0338, wR₂=0.0965
R indices(all data)	R₁=0.0372, wR₂=0.0987
Largest diff. peak and hole/(e·nm^-3)	1204, -721

Fig.1 Experimental(a) and simulated(b) XRD patterns of JU94

Fig.2 Thermal ellipsoids of JU94 given at 30% probabilitySymmetry codes: #1. -x+2, y-1/2, -z+3/2; #2. -x+2, y+1/2, -z+3/2; #3. x+1, y, z+1; #4. -x+3, -y+2, -z+2; #5. x+1, -y+3/2, z+1/2; #6. x, -y+3/2, z-1/2.

Fig.3 Tetranuclear iron cluster(Fe4P6O30H4) in JU94(A), the layer formed by clusters through sharing PO4 tetrahedra(B) and 3D framework constructed by the layers linked through O atoms(C)

Fig.4 Framework of JU94 viewed along [101](A) and [1ˉ01](B) directions and the channel along [[101]] or [1ˉ01] direction(C)

Fig.5 Framework of JU94 viewed along [010](A) and [111](B) directions

Fig.6 57Fe Mössbauer spectra of JU94

Table 2 Parameters obtained in Mössbauer analysis*

Absorption peak	IS/(mm·s^-1)	QS/(mm·s^-1)	HWHM/(mm·s^-1)	Area fraction(%)
1	0.40±0	0.36±0	0.19±0	51.4
2	0.42±0	0.67±0	0.18±0	48.6

Fig.7 Variable-temperature magnetic susceptibilities of JU94

参考文献 29

[1]	Wilson S. T., Lok B. M., Messina C. A., Marcus B. K., Patton R. L., Flanigen E. M., J. Am. Chem. Soc., 1982, 104, 1146—1147
[2]	Lu H. Y., Tong X. Q., Yan Y., Yan W. F., Yu J. H., Xu R. R., Chem. J. Chinese Universities,2013, 34(7), 1571—1575
	(卢慧英, 仝晓强, 颜岩, 闫文付, 于吉红, 徐如人. 高等学校化学学报, 2013, 34(7), 1571—1575)
[3]	Yu J. H., Xu R. R., Acc. Chem. Res., 2010, 43, 1195—1204
[4]	Li Y., Yu J. H., Xu R. R., Baerlocher C., McCusker L. B., Angew. Chem. Int. Ed., 2008, 47, 4401—4405
[5]	Li Y., Yu J. H., Xu R. R., Angew. Chem. Int. Ed., 2013, 52, 1673—1677
[6]	Yu J. H., Xu R. R., Chem. Soc. Rev., 2006, 35, 593—604
[7]	Song X., Li Y., Gan L., Wang Z., Yu J., Xu R., Angew. Chem. Int. Ed., 2008, 48, 314—317
[8]	Rao C. N. R., Natarajan S., Choudhury A., Neeraj S., Ayi A. A., Acc. Chem. Res., 2001, 34, 80—87
[9]	Yang G. Y., Sevov S. C., J. Am. Chem. Soc., 1999, 121, 8389—8390
[10]	Thirumurugan A., Natarajan S., Dalton Trans., 2003, 17, 3387—3391
[11]	Du Y., Yu J. H., Wang Y., Pan Q. H., Zou Y. C., Xu R. R., J. Solid State Chem., 2004, 177, 3032—3037
[12]	Sassoye C., Marrot J., Loiseau T., Loiseau T., Férey G., Chem. Mater., 2002, 14, 1340—1347
[13]	Beitone L., Marrot J., Loiseau T., Férey G., Henry M., Huguenard C., Gansmuller A., Taulelle F., J. Am. Chem. Soc., 2003, 125, 1912—1922
[14]	Lin C. H., Wang S. N., Lii K. H., J. Am. Chem. Soc., 2001, 123, 4649—4650
[15]	Soghomonian V., Chen Q., Haushalter R.C., Zubieta J., Charles J. O., Science, 199,259, 1596—1599
[16]	Khan M. I., Meyer L. M., Haushalter R. C., Schweitzer A. L., Zubieta J., Dye J. L., Chem. Mater., 1996, 8, 43—53
[17]	Murugavel R., Choudhury A., Walawalkar M. G., Pothiraja R., Rao C. N. R., Chem. Rev., 2008, 108, 3549—3655
[18]	Choudhury A., Rao C. N. R., J. Struct. Chem., 2002, 43, 632—642
[19]	Cavellec M., Grenèche J. M., Riou D., Férey G., Chem. Mater., 1998, 10, 2434—2439
[20]	Cavellec M., Riou D., Férey G., Acta Crystallogr., 1994, C50, 1379—1381
[21]	Choudhury A., Natarajan S., Rao C. N. R., Chem. Commun., 1999, 14, 1305—1306
[22]	Armas S. F., Mesa J. L., Pizarro J. L., Garitaonandia J. S., Arriortua M. I., Rojo T., Angew. Chem. Int. Ed., 2004, 43, 977—980
[23]	Rhule J. T., Hill C. L. , Jadd C. L., Schinazi R. F., Chem. Rev., 1998, 98, 327—358
[24]	Rowan E., Nolte R. J. M., Angew. Chem. Int. Ed. Engl., 1998, 37, 63—68
[25]	Kagan R., Mitzi D. B., Dimitrakopoulos C. D., Science,1999, 286, 945—947
[26]	Knof U., Zelewsky A. V., Angew. Chem. Int. Ed. Engl., 1999, 38, 302—322
[27]	Bruker AXS Inc., SAINT, Madison, WI, 2000
[28]	Bruker AXS Inc., SHELXTL, Madison, WI, 2000
[29]	Zima V., Lii K., J. Chem. Soc.,Dalton Trans., 1998, (24), 4109—4112

开放骨架磷酸铁的合成与性质

Synthesis and Characterization of a New Open-framework Iron Phosphate^†

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开放骨架磷酸铁的合成与性质

Synthesis and Characterization of a New Open-framework Iron Phosphate†

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Synthesis and Characterization of a New Open-framework Iron Phosphate^†