基于环糊精的介孔碳材料的制备及催化性能

doi:10.7503/cjcu20160216

摘要/Abstract

摘要：

以羟丙基-β-环糊精为结构导向剂, 正硅酸乙酯为硅前驱物, 通过高氯酸铵氧化联合硬模板技术合成了一系列孔径可调的介孔碳材料. 采用氮气吸附-脱附实验、透射电子显微镜(TEM)、 X射线衍射分析仪(XRD)和傅里叶变换红外光谱(FTIR)对碳材料的结构和表面化学性质进行了表征; 并以水合肼还原对硝基甲苯反应为模型, 研究了介孔碳材料对硝基芳烃还原反应的催化性能. 实验结果表明, 所得材料具有蠕虫状孔系结构, 有较高的比表面积和孔容、较窄的孔径分布范围、较多的含氧官能团和较高的催化活性; 且以高氯酸铵室温氧化合成的介孔碳的催化活性最高, 产物收率达到88.48%; 介孔碳循环使用4次后仍然保持良好的催化活性.

关键词: 羟丙基-β-环糊精, 介孔碳, 高氯酸铵氧化, 硝基芳烃, 催化性能

Abstract:

Mesoporous carbons with tailored pore size were prepared by technologies of ammonium perchlorate oxidation and hard template with hydroxypropyl-β-cyclodextrin as the structure-director and tetraethoxysilane as the silica precursor. The structures and surface chemistry properties of these carbon materials were characterized by N₂ adsorption, TEM, XRD and FTIR measurements. Their catalytic performances were investigated through the reduction of nitroaromatic using hydrazine hydrate as the reducing agent. The results showed that mesoporous carbon materials prepared using hydroxypropyl-β-cyclodextrin-based silicas as inorganic templates synthesized by ammonium perchlorate oxidation have worm-like pore structure and higher catalytic activity, especially mesoporous carbon prepared through oxidation under room temperature, the yield of p-methylaniline is 88.48% in the presence of the catalyst, and it still keeps higher activity after being reused for 4 times through a simple filtration, washed with ethanol and dried. Higher surface area and pore volume, and the presence of abundant surface oxygen-containing functional groups, which originates from the special preparation process of carbon material, are likely responsible for the high catalytic property of these mesoporous carbon materials.

Key words: Hydroxypropyl-β-cyclodextrin, Mesoporous carbon, Ammonium perchlorate oxidation, Nitroaromatic, Catalytic performance

中图分类号:

O643.36

TrendMD:

王慧春, 王发春, 李宝林. 基于环糊精的介孔碳材料的制备及催化性能. 高等学校化学学报, 2016, 37(11): 2076.

WANG Huichun, WANG Fachun, LI Baolin. Preparation of Cyclodextrin-based Mesoporous Carbon and Its Catalytic Performance^†. Chem. J. Chinese Universities, 2016, 37(11): 2076.

图/表 13

参考文献 33

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Sample	S_BET/(m²·g^-1)	S_mic/(m²·g^-1)	V_t/(cm³·g^-1)	V_mic/(cm³·g^-1)	D_BJH/nm
MS-cal	171	2	0.12	0.0005	3.5
MS-rt	848	5	0.33	0.0050	3.4
MS-60	849	3	0.58	0.0050	3.5
MS-80	782	13	1.11	0.0070	4.8
MS-100	594	39	1.32	0.0170	6.0

Sample	S_BET/(m²·g^-1)	S_mic/(m²·g^-1)	V_t/(cm³·g^-1)	V_mic/(cm³·g^-1)	D_BJH/nm
MS-cal	171	2	0.12	0.0005	3.5
MS-rt	848	5	0.33	0.0050	3.4
MS-60	849	3	0.58	0.0050	3.5
MS-80	782	13	1.11	0.0070	4.8
MS-100	594	39	1.32	0.0170	6.0

Sample	S_BET/(m²·g^-1)	S_mic/(m²·g^-1)	V_t/(cm³·g^-1)	V_mic/(cm³·g^-1)	V_mes/(cm³·g^-1)	D_BJH/nm
MC-cal	562	376	0.38	0.20	0.18	3.9
MC-rt	1240		1.33		1.33	3.9
MC-60	1430		1.52		1.52	3.3
MC-80	1407		1.58		1.58	3.3
MC-100	1222	154	1.74	0.07	1.67	3.7

Sample	S_BET/(m²·g^-1)	S_mic/(m²·g^-1)	V_t/(cm³·g^-1)	V_mic/(cm³·g^-1)	V_mes/(cm³·g^-1)	D_BJH/nm
MC-cal	562	376	0.38	0.20	0.18	3.9
MC-rt	1240		1.33		1.33	3.9
MC-60	1430		1.52		1.52	3.3
MC-80	1407		1.58		1.58	3.3
MC-100	1222	154	1.74	0.07	1.67	3.7

Sample	Time^b/min	Yield^c(%)	Sample	Time^b/min	Yield^c(%)
Without any catalysts	720	0	MC-60	240	85.23±0.11
Activated carbon	720	0	MC-80	300	83.72±0.21
MC-cal	480	71.68±0.12	MC-100	180	82.95±0.24
MC-rt	30	88.48±0.17