H6P2Mo18O62/Zn(BDC)(Bipy)0.5复合材料的合成、 表征及对亚甲基蓝的吸附

doi:10.7503/cjcu20160253

摘要/Abstract

摘要：

在溶剂热条件下, 以H₆P₂Mo₁₈O₆₂、对苯二甲酸(H₂BDC)、 4,4'-联吡啶(Bipy)和硝酸锌为原料构筑了1个三维金属有机骨架复合材料H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5, 并采用红外光谱(IR)、 X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TG)、 N₂吸附-脱附等手段对产物进行了表征. 同时, 研究了产物对水溶液中亚甲基蓝(MB)的吸附性能, 并探讨了MB初始pH值、初始浓度和温度对吸附量的影响. 结果表明, 产物的等温吸附模型符合Langmuir等温吸附模型, 动力学符合拟二级动力学. H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5对亚甲基蓝的吸附是自发和放热的, 此外, 产物对甲基紫、罗丹明B、孔雀石绿等阳离子染料也具有良好的吸附性能.

关键词: 三维金属有机骨架, H6P2Mo18O62, 吸附, 分离, 染料

Abstract:

By employing the H₆P₂Mo₁₈O₆₂, terephthalic acid(H₂BDC), 4,4'-bipyridine(Bipy) to assemble with Zn²⁺ ion, a three-dimensional(3D) metal organic framework composite, named H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5, was synthesized. The composition, structure, morphology, stability and toleration of H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5 were characterized by X-ray powder diffraction pattern(XRD), Fourier transform infrared(FTIR) spectrum, scanning electron microscopy(SEM), thermogravimetric(TG) analysis and N₂ adsorption-desorption analysis. The adsorption of methylene blue(MB) onto H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5 in aqueous solution was studied. The effects of the experimental parameters including the temperature, the initial pH value and initial concentration of methylene blue solution were discussed. The experimental data could be well described by the Langmuir equations and pseudo-second-order kinetic model. The adsorption process of methylene blue on the composite was spontaneous and exothermic. Furthermore, we also explored the adsorption properties of H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5 to methyl violet, malachite green, rhodamine B, and methyl orange. The results indicated that this new absorbent showed better adsorption performance towards cationic dyes.

Key words: Three-dimensional(3D) metal organic framework, H6P2Mo18O62, Adsorption, Separation, Dye

中图分类号:

O614.6

龚文朋, 田超强, 杜晓刚, 杨水金. H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5复合材料的合成、表征及对亚甲基蓝的吸附[J]. 高等学校化学学报, 2016, 37(9): 1596-1604.

GONG Wenpeng, TIAN Chaoqiang, DU Xiaogang, YANG Shuijin. Synthesis and Characterization of Composite H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5 and Its Adsorption Activity for Methylene Blue^†[J]. Chemical Journal of Chinese Universities, 2016, 37(9): 1596-1604.

图/表 17

Fig.1 FTIR spectra of H6P2Mo18O62(a), Zn(BDC)(Bipy)0.5(b) and H6P2Mo18O62/Zn(BDC)(Bipy)0.5(c)

Fig.2 XRD patterns of H6P2Mo18O62(a), Zn(BDC)(Bipy)0.5(b) and H6P2Mo18O62/Zn(BDC)(Bipy)0.5(c)

Table 1 Elemental analysis of Zn(BDC)(Bipy)0.5 and H6P2Mo18O62/Zn(BDC)(Bipy)0.5

Sample	Element	w(%)	n(Mo):n(P)
H₆P₂Mo₁₈O₆₂	P	2.13	9.1
	Mo	60.02
	Zn	0
H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5	P	1.74	9.0
	Mo	48.59
	Zn	20.61

Fig.3 TG curves of Zn(BDC)(Bipy)0.5(a) and H6P2Mo18O62/Zn(BDC)(Bipy)0.5(b)

Fig.4 Nitrogen adsorption isotherms of Zn(BDC)(Bipy)0.5 and H6P2Mo18O62/Zn(BDC)(Bipy)0.5

Table 2 Structural properties of Zn(BDC)(Bipy)0.5 and H6P2Mo18O62/Zn(BDC)(Bipy)0.5

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	D/nm
Zn(BDC)(Bipy)_0.5	710.6	0.32	1.79
H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5	249.9	0.12	1.92

Fig.5 SEM images of H6P2Mo18O62(A), Zn(BDC)(Bipy)0.5(B) and H6P2Mo18O62/Zn(BDC)(Bipy)0.5(C)

Fig.6 Effect of pH values on adsorption capacities for MB

Fig.7 Effect of initial mass concentration on adsorption capacities for MB Initial mass concentration of MB/(mg·mL-1): a. 40;b. 60; c. 80; d. 100; e. 120; f. 140.

Fig.8 Effect of temperature on adsorption capacity for MB

Fig.9 Comparison of adsorption activity of H6P2Mo18O62(a), Zn(BDC)(Bipy)0.5(b) and H6P2Mo18O62/Zn(BDC)(Bipy)0.5(c)

Fig.10 Adsorption amounts of different dyes on H6P2Mo18O62/Zn(BDC)(Bipy)0.5

Fig.11 Selective adsorption capability of H6P2Mo18O62/Zn(BDC)(Bipy)0.5 to the mixed dyes solution

Table 3 Parameters of pseudo-first-order and pseudo-second-order adsorption kinetics model in different initial concentrations

Kinetics model	Initial concentration of MB/ (mg·L^-1)	Q_e,exp/ (mg·g^-1)	Q_e,cal/ (mg·g^-1)	K₁/min^-1 or K₂/ (g·mg^-1·min^-1)	R²
Pseudo-first-order model	90	179.43	1.1693	0.09343	0.9661
	100	198.64	1.7124	0.10918	0.9669
Pseudo-second-order model	90	179.43	179.53	0.000021	1
	100	198.64	198.81	0.0000157	1

Fig.12 Langmuir isotherm of methylene blue adsorption onto H6P2Mo18O62/Zn(BDC)(Bipy)0.5

Table 4 Isotherm parameters of the adsorption of methylene blue by H6P2Mo18O62/Zn(BDC)(Bipy)0.5 at different temperature

Temperature/K	Langmuir				Freundlich
Temperature/K	Q_m/(mg·g^-1)	K_L/(L·mg^-1)	R_L	R²	K_F/(mg·g^-1)	n	R²
293	277.78	0.00319	0.7337	0.9986	244.84	13.18	0.9606
303	275.48	1.9621	0.00459	0.9893	194.54	7.76	0.9137
313	273.22	0.7205	0.01242	0.9695	157.66	5.76	0.7916

Table 5 Thermodynamic parameters of adsorption methylene blue onto H6P2Mo18O62/Zn(BDC)(Bipy)0.5

ΔG^o/(kJ·mol^-1)			ΔH^o/(kJ·mol^-1)	ΔS^o/(J·mol^-1·K^-1)
293 K	303 K	313 K	ΔH^o/(kJ·mol^-1)	ΔS^o/(J·mol^-1·K^-1)
-14.87	-11.33	-9.5	-93.81	-270.31

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H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5复合材料的合成、表征及对亚甲基蓝的吸附

Synthesis and Characterization of Composite H₆P₂Mo₁₈O₆₂/Zn(BDC)(Bipy)_0.5 and Its Adsorption Activity for Methylene Blue^†

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