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第 35 卷第 9 期 精 细 化 工 Vol.35, No.9
201 8 年 9 月 FINE CHEMICALS Sept. 2018

催化与分离提纯技术
氨水改性氧化石墨烯高效催化

Knoevenagel 缩合反应

薛 冰，刘香梅，柳 娜，朱家贵，李永昕

（常州大学 石油化工学院 江苏省绿色催化材料与技术重点实验室，江苏 常州 213164）

摘要：通过浸渍法制备了氨水改性氧化石墨烯，考察了其在苯甲醛和丙二腈的 Knoevenagel 缩合反应中的催化
性能。通过 X 射线粉末衍射（XRD）、拉曼光谱（Raman）、傅里叶变换红外光谱（FTIR）、NH 3 程序升温脱附
（NH 3 -TPD）、元素分析等对催化剂进行了表征，考察了工艺条件对其催化剂性能的影响。结果表明：氨水改性
+
氧化石墨烯可以有效地将 NH 4 固载于氧化石墨烯表面；氧化石墨烯经氨水改性后在苯甲醛和丙二腈的
Knoevenagel 缩合反应中表现出良好的催化性能，随着改性实验中氨水质量分数的增加，催化剂的活性不断增加。
以质量分数 5%的氨水为改性剂制备的催化剂（AW-GO-5%）在 60 ¥、4 h 下催化苯甲醛和丙二腈的 Knoevenagel
缩合反应，苯甲醛的转化率高达 93.6%，产物苄亚基丙二腈的选择性为 94.8%，该催化剂重复使用 4 次后催化活
性仍较高。
关键词：氧化石墨烯；氨水；改性；羧酸铵；Knoevenagel 缩合；催化技术
中图分类号：TQ241.1 文献标识码：A 文章编号：1003-5214 (2018) 09-1529-07

Highly Efficient Aqueous Ammonia Modified Graphene Oxide for

Knoevenagel Condensation

XUE Bing, LIU Xiang-mei, LIU Na, ZHU Jia-gui, LI Yong-xin
（Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou
University, Changzhou 213164, Jiangsu, China）

Abstract: A series of aqueous ammonia modified graphene oxide samples were prepared by impregnation
method and used to catalyze Knoevenagel condensation reaction between benzaldehyde and malononitrile.
The prepared materials were characterized by X-ray diffraction, Raman spectra, Fourier transform infrared
spectroscopy, NH 3-TPD and elemental analysis. Moreover, the influence of technological conditions on the
+
performance of catalyst was investigated. The results indicated that NH 4 was successfully immobilized on
the surface of graphene oxide. The aqueous ammonia modified graphene oxide samples exhibited excellent
catalytic performances in the Knoevenagel condensation reaction between benzaldehyde and malononitrile.
The catalytic activity increased gradually with increasing the concentration of aqueous ammonia. 93.6%
benzaldehyde conversion and 94.8% benzylidene malononitrile selectivity were obtained when the reaction
was carried out at 60 ¥ for 4 h in the presence of aqueous ammonia (5% mass fraction) modified graphene
oxide (AW-GO-5%). Catalytic activity was still excellent after the AW-GO-5% catalyst could be recycled
four times.
Key words: graphene oxide; aqueous ammonia; modification; ammonium carboxylate; Knoevenagel
condensation; catalysis technology
Foundation items: National Natural Science Foundation of China (21376032,21673024)

收稿日期：2017-08-17; 定用日期：2017-12-22; DOI: 10.13550/j.jxhg.20170674
基金项目：国家自然科学基金（21376032，21673024）
作者简介：薛 冰（1978—），男，博士，副研究员，电话 0519-86330332，E-mail：xuebing@cczu.edu.cn