新型过渡金属取代层状磷酸铝[C4H11N]0.77[C4H12N]0.23[C3H12N2]2[H3O]2·[Co0.23Al5.77P8O32]的共模板法合成及表征

doi:10.7503/cjcu20140206

摘要/Abstract

摘要：

采用共模板法以二乙胺和1,2-丙二胺为模板剂, 合成了过渡金属取代的二维层状磷酸铝化合物[C₄H₁₁N]_0.77[C₄ $H 1 2$ N]_0.23[C₃H₁₂N₂]₂[C $o 0.2 3$ Al_5.77P₈O₃₂][H₃O]₂(1). 通过X射线衍射(XRD)、热重分析(TG)、元素分析(ICP-AES及CHN)、固体紫外-可见分析(Solid-UV-Vis)及扫描电子显微镜(SEM)等对化合物1进行了表征. 该化合物属三斜晶系, P $1 -$ 空间群, 晶胞参数a=0.95029(19) nm, b=1.2689(3) nm, c=1.2987(3) nm, α=118.70(3)°, β=97.64(3)°, γ=99.72(3)°, V=1.3117(5) nm³, Z=1. 其无机骨架由铝(或钴)氧四面体(AlO₄或CoO₄)和磷氧四面体PO₃(=O)严格交替连接形成4,6,12-网层结构, 无机层沿[001]方向堆砌成一维十二元环孔道. Co无序取代Al的位置, 其Co/Al摩尔比约为1∶25.1. 运用分子动力学模拟的方法, 通过计算有机模板剂和无机骨架的相互作用, 讨论了2种有机胺分子的共模板作用.

关键词: 杂原子取代磷酸铝, 层状结构, 溶剂热合成, 共模板作用

Abstract:

In the presence of diethylamine and 1,2-diaminopropane, a new microporous cobalt-containing aluminophosphate compound [C₄H₁₁N]_0.77[C₄H₁₂N]_0.23[C₃H₁₂N₂]₂[H₃O]₂[C $o 0.2 3$ Al_5.77P₈ $O 3 2$ ](1) was synthesized. The structure of compound 1 was determined by single-crystal X-ray diffraction(XRD) analysis and further characterized by X-ray powder diffraction, thermogravimetric analysis(TG/DTA), inductively coupled atomic emission spectrometry(ICP-AES), CHN, Solid-UV-Vis spectrometry and scanning electron microscopy(SEM). It crystallizes in the triclinic system, space group P $1 -$ , with a=0.95029(19) nm, b=1.2689(3) nm, c=1.2987(3) nm, α=118.70(3)°, β=97.64(3)°, γ=99.72(3)°, V=1.3117(5) nm³, Z=1. The structure are built up from strict alternation of CoO₄/AlO₄and PO₃(=O) units. It contains 12-membered ring channel along [001] direction. The molar ratio of Co to Al is 1∶25.1. We also calculated the interaction energy and studied the co-template role of those two amines by the molecular dynamics method.

Key words: Heteroatom containing aluminophosphate, Layered structure, Solvothermal synthesis, Co-template role

中图分类号:

O611.4

TrendMD:

朱靖然, 李柯, 颜岩, 李旭, 宋晓伟. 新型过渡金属取代层状磷酸铝[C₄H₁₁N]_0.77[C₄H₁₂N]_0.23[C₃H₁₂N₂]₂[H₃O]₂·[Co_0.23Al_5.77P₈O₃₂]的共模板法合成及表征. 高等学校化学学报, 2014, 35(6): 1130.

ZHU Jingran, LI Ke, YAN Yan, LI Xu, SONG Xiaowei. Co-templates Synthesis and Characterization of a New Two-dimensional Co-containing Aluminophosphate [C₄ $H 1 1$ N]_0.77[C₄ $H 1 2$ N]_0.23[C₃H₁₂N₂]₂[H₃O]₂[Co_0.23Al_5.77P₈ $O 3 4$ ]^†. Chem. J. Chinese Universities, 2014, 35(6): 1130.

图/表 7

Table 1 Crystal data and structure refinement parameters for compound 1

Empirical formula	C₁₀H_41.23Al_5.77 Co_0.23N₅O₃₄P₈	Calculated density/(Mg·m^-3)	1.479
Crystal system	Triclinic	Absorption coefficient/mm^-1	0.456
Space group	P $1 -$	F(000)	589
a/nm	0.95029(19)	Limiting indices	-12≤h≤12,-15≤k≤16,-16≤l≤16
b/nm	1.2689(3)	Reflections collected/unique[R(int)=0.0442]	12505/5845
c/nm	1.2987(3)	Refinement method	Full-matrix least-squares on F²
α/(°)	118.70(3)	Data/restraints/parameters	5845/82/355
β/(°)	97.64(3)	Goodness-of-fit on F²	1.083
γ/(°)	99.72(3)	Final R indices [I > 2σ(I)]	R₁=0.0532, wR₂=0.1678
V/nm³, Z	1.3117(5), 1	R indices(all data)	R₁=0.0621, wR₂=0.1771

Table 1 Crystal data and structure refinement parameters for compound 1

Empirical formula	C₁₀H_41.23Al_5.77 Co_0.23N₅O₃₄P₈	Calculated density/(Mg·m^-3)	1.479
Crystal system	Triclinic	Absorption coefficient/mm^-1	0.456
Space group	P $1 -$	F(000)	589
a/nm	0.95029(19)	Limiting indices	-12≤h≤12,-15≤k≤16,-16≤l≤16
b/nm	1.2689(3)	Reflections collected/unique[R(int)=0.0442]	12505/5845
c/nm	1.2987(3)	Refinement method	Full-matrix least-squares on F²
α/(°)	118.70(3)	Data/restraints/parameters	5845/82/355
β/(°)	97.64(3)	Goodness-of-fit on F²	1.083
γ/(°)	99.72(3)	Final R indices [I > 2σ(I)]	R₁=0.0532, wR₂=0.1678
V/nm³, Z	1.3117(5), 1	R indices(all data)	R₁=0.0621, wR₂=0.1771

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

Fig.2 SEM image of compound 1

Fig.3 Asymmetric unit of compound 1(without diethylamine) The thermal ellipsoids are shown at 50% probability.

Fig.4 Framework of compound 1 viewed along [001] direction

Fig.5 TG(a) and DTA(b) curves of compound 1

Fig.6 Solid-UV-Vis spectrum of compound 1

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新型过渡金属取代层状磷酸铝[C₄H₁₁N]_0.77[C₄H₁₂N]_0.23[C₃H₁₂N₂]₂[H₃O]₂·[Co_0.23Al_5.77P₈O₃₂]的共模板法合成及表征

Co-templates Synthesis and Characterization of a New Two-dimensional Co-containing Aluminophosphate [C₄ $H 1 1$ N]_0.77[C₄ $H 1 2$ N]_0.23[C₃H₁₂N₂]₂[H₃O]₂[Co_0.23Al_5.77P₈ $O 3 4$ ]^†

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