水体系中尿素卤化铵共晶合成及影响因素的理论研究

doi:10.7503/cjcu20180481

摘要/Abstract

摘要：

通过缓慢蒸发技术合成尿素氯化铵、尿素溴化铵和尿素氟化铵3种尿素卤化铵共晶. 采用第一性原理方法, 在原尿素氯化铵晶胞结构基础上, 构建同晶系的尿素氟化铵及尿素溴化铵共晶晶胞, 并对3种尿素卤化铵共晶结构的稳定性、堆积系数和形成能、卤素离子半径和电负性及离子水合作用进行对比研究. 结果表明, 对于尿素溴化铵共晶, Br^-半径较大导致晶胞内部空腔变形, 溴离子水合团簇稳定, 均会阻碍Br^-进入尿素孔道内; 对于尿素氟化铵共晶, F^-的强电负性使氟离子水合团簇F^-(H₂O)₅稳定性很强, 阻碍裸F^-进入尿素空腔中; 对于易于合成的尿素氯化铵共晶, 由于Cl^-的电负性及半径大小都适中, 水合离子团簇的稳定性适当, 易于进入尿素空腔中.

关键词: 尿素共晶, 卤化铵, 影响因素, 理论计算

Abstract:

Three urea ammonium halide cocrystals were synthesized by slow evaporation technique. It was found that the urea ammonium chloride was still easy to synthesize than the other two urea ammonium halide. The first-principles method was used to construct isomorphous urea ammonium fluoride and urea ammonium bromide cocrystal unit cell based on the original unit structure of urea ammonium chloride. The stability, packing coefficient, formation energy of the three urea ammonium halide cocrystal structures, halogen ion radius and electronegativity, and ionic hydration energy were compared. The results showed that for the urea ammonium bromide cocrystal, the larger Br^-radius leads to the deformation of the internal cavity of the urea cell, and the hydrated cluster of bromide ions is stable, which will hinder the entry of Br^- into the urea channel; for urea ammonium fluoride cocrystal, the electronegativity of F^-makes the fluoride ion hydrate cluster F^-(H₂O)₅ very stable, preventing the bare F^- entering the urea cavity; for the urea ammonium chloride cocrystal, the electronegativity and radius size of Cl^- are both moderate, the stability of hydrated ion clusters is appropriate, all these factors make it easy to enter the urea cavity.

Key words: Urea cocrystal, Ammonium halide, Influence factor, Theoretical calculation

中图分类号:

O641

TrendMD:

闫璇, 薛冰纯, 刘二保. 水体系中尿素卤化铵共晶合成及影响因素的理论研究. 高等学校化学学报, 2018, 39(12): 2700.

YAN Xuan,XUE Bingchun,LIU Erbao. Synthesis of Urea Ammonium Halide Cocrystal and Theoretical Study of Its Influencing Factors in Water System^†. Chem. J. Chinese Universities, 2018, 39(12): 2700.

图/表 11

参考文献 26

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Method	a/nm	b/nm	c/nm	α/(°)	β/(°)	γ/(°)	Volume/nm³
Solid phase honey-like channel method^[21]	0.7923	1.7121	0.8072	90	90	90	1.0950
Slow evaporation method	0.7927	1.7152	0.8050	90	90	90	1.0945

Method	a/nm	b/nm	c/nm	α/(°)	β/(°)	γ/(°)	Volume/nm³
Solid phase honey-like channel method^[21]	0.7923	1.7121	0.8072	90	90	90	1.0950
Slow evaporation method	0.7927	1.7152	0.8050	90	90	90	1.0945

Species	a/nm	b/nm		c/nm		d(H1—H2)/nm		d(N1—N2)/nm		d(X1—H4)/nm
Urea-NH₄F	0.7533	1.6318		0.8069		0.3433		0.3179		0.1709
Urea-NH₄Cl	0.8082	1.7301		0.8580		0.3998		0.3417		0.2253
Urea-NH₄Br	0.8250	1.7844		0.8875		0.4171		0.3438		0.2425
Species	d(X1—X4)/nm		d(X2—X3)/nm		d(C2—C3)/nm		d(O1—O2)/nm		ÐH3—N3—H4/(°)		ÐH4—N3—H5/(°)
Urea-NH₄F	0.4690		0.4370		0.4343		0.4506		110.976		111.331
Urea-NH₄Cl	0.5315		0.5075		0.4937		0.4830		108.549		110.592
Urea-NH₄Br	0.5476		0.5220		0.5025		0.4892		108.162		110.392

Species	a/nm	b/nm		c/nm		d(H1—H2)/nm		d(N1—N2)/nm		d(X1—H4)/nm
Urea-NH₄F	0.7533	1.6318		0.8069		0.3433		0.3179		0.1709
Urea-NH₄Cl	0.8082	1.7301		0.8580		0.3998		0.3417		0.2253
Urea-NH₄Br	0.8250	1.7844		0.8875		0.4171		0.3438		0.2425
Species	d(X1—X4)/nm		d(X2—X3)/nm		d(C2—C3)/nm		d(O1—O2)/nm		ÐH3—N3—H4/(°)		ÐH4—N3—H5/(°)
Urea-NH₄F	0.4690		0.4370		0.4343		0.4506		110.976		111.331
Urea-NH₄Cl	0.5315		0.5075		0.4937		0.4830		108.549		110.592
Urea-NH₄Br	0.5476		0.5220		0.5025		0.4892		108.162		110.392

Atom	Urea-NH₄F			Urea-NH₄Cl			Urea-NH₄Br
Atom	x/nm	y/nm	z/nm	x/nm	y/nm	z/nm	x/nm	y/nm	z/nm
H1	0.0272	0.0661	0.0436	0.0253	0.0667	0.0437	0.0247	0.0667	0.0432
H2	0.0728	0.0661	0.0436	0.0747	0.0667	0.0437	0.0753	0.0667	0.0432
N1	0.0153	0.0691	0.0425	0.0143	0.0695	0.0422	0.0140	0.0694	0.0415
N2	0.0347	0.0691	0.0075	0.0357	0.0695	0.0078	0.0360	0.0694	0.0086
X1	0.0500	0.0632	0.0577	0.0500	0.0617	0.0549	0.0500	0.0616	0.0547
H4	0.0337	0.0579	0.0678	0.0320	0.0540	0.0676	0.0315	0.0532	0.0676
X2	0.0500	0.0862	0.0113	0.0500	0.0881	0.0071	0.0500	0.0883	0.0070
X3	0	0.0862	0.0387	0	0.0881	0.0429	0	0.0883	0.0430
C2	0.0500	0.0849	0.0616	0.0500	0.0843	0.0585	0.0500	0.0843	0.0588
C3	0	0.0849	0.0884	0	0.0843	0.0915	0	0.0843	0.0912
X4	0	0.0632	0.0923	0	0.0617	0.0951	0	0.0616	0.0953
O1	0.0500	0.05670	0.0097	0.0500	0.0581	0.0096	0.0500	0.0584	0.0102
O2	0	0.0570	0.0403	0	0.0581	0.0404	0	0.0584	0.0398